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  • Chemistry  (51,082)
  • Inorganic Chemistry  (3,618)
  • Engineering  (3,361)
  • GEOPHYSICS  (3,293)
  • 2015-2019  (285)
  • 1990-1994  (57,456)
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  • 1
    Publication Date: 2021-05-19
    Description: Aleksey Sergeevich Vinnov (25.05.1958 – 04.06.2019) was a Candidate of Sciences (Engineering), an Associate Professor, a talented lecturer, a rector of the Kerch Maritime Technological Institute (KMTI) in 2000–2005, a Senior Researcher in the FSBSI “Southern Scientific Research Institute of Marine Fisheries and Oceanography” (YugNIRO), and a Deputy Head for Operation and Quality of the Limited Liability Company under the Laws of Russian Federation “Aquamarine”. A.S. Vinnov made a great contribution into the development of education and science in the field of fisheries. Aleksey Sergeevich began his professional life as a Junior Researcher in the Astrakhan Technical Institute of Fishing Industry and Economy and defended his Candidate's Thesis in 1988. He dedicated the major part of his working career to the Kerch State Maritime Technological University, where he had been employed for 21 years, taking positions from a senior lecturer of the Department of Fish Processing Technology, an Associate Professor, the Dean of the Technological Faculty, the vice-rector for academic affairs, to the rector of the University. A.S. Vinnov was known for his rational thinking and professional integrity; he was diplomatic and considerate, and proved to be a competent leader. Vinnov's research works were dedicated to the issues of development of production technology for canned fish and fish protein mass, of kinetics of enzymatic hydrolysis, and many other subjects. A.S. Vinnov was honored with several badges of distinction due to his high professional expertise and personal contribution to the development of fisheries field, particularly education.
    Description: Алексей Сергеевич Виннов (25.05.1958 – 04.06.2019 гг.) — кандидат технических наук, доцент, талантливый преподаватель, ректор Керченского морского технологического института с 2000 по 2005 г. (КМТИ), старший научный сотрудник ФГБНУ «Южный научно-исследовательский институт рыбного хозяйства и океанографии» (ЮгНИРО), заместитель директора по производству и качеству ООО «Аквамарин». А.С. Виннов внес огромный вклад в развитие образования и науки рыбной отрасли. Свою трудовую деятельность Алексей Сергеевич начал в должности младшего научного сотрудника Астраханского технического института рыбной промышленности и хозяйства, успешно защитив в 1988 г. кандидатскую диссертацию. Большую часть своей трудовой деятельности он посвятил Керченскому государственному морскому технологическому университету, проработав здесь 21 год в должностях от старшего преподавателя кафедры технологии рыбных продуктов, доцента, декана технологического факультета, проректора по учебной работе до ректора университета. А.С. Виннов обладал рациональным мышлением, был очень грамотным, тактичным человеком, умелым руководителем. Научная деятельность Алексея Сергеевича была посвящена изучению вопросов усовершенствования технологии рыбных консервов, рыбных белковых масс, кинетики ферментативного гидролиза, а также многим другим. За личный вклад в развитие образования и рыбной отрасли, за высокий профессионализм А.С. Виннов был удостоен ряда почетных знаков отличия.
    Description: Published
    Keywords: Researchers ; Engineering ; Fish processing ; Canned food ; Rector ; Proteins ; Hydrolysis
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.91-95
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  • 2
    Publication Date: 2021-05-19
    Description: 0Genetic polymorphism by means of biochemical genetic markers using polyacrylamide gel electrophoresis system in four barbus fish species has been investigated. Species scientific name were Barbus sharpeyi ; Gunther, 1847 , Barbus grypus ; Heckel, 1843, Barbus xanthopterus ; Heckel, 1843 and Barbus esocinus ; Heckel, 1843.Sampling site and location were mainly in the rivers located in Khoozestan province such as Karoon and Karkheh rivers and the Dez dam. Different organs such as blood, muscle, kidney, eye and heart were sampled and analysed for the presence of tf, es, sod and pgm alleles. High polymorphism and presence of different alleles scored, but populations were not in the H-W equilibrium. Considring results, using current and avaiable genetic markers such as microsattelits is recommended for future works.
    Description: Iranian Fisheries Science Research Institute
    Description: Published
    Keywords: Chemistry ; Genetics ; Genetics Markers ; Distinguish ; Barbus ; Species ; Barbus sharpeyi ; Barbus xanthopterus ; Barbus esocinus
    Repository Name: AquaDocs
    Type: Report , Refereed
    Format: 62pp.
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  • 3
    Publication Date: 2021-05-19
    Description: Cheshmehkileh River and adjacent mountainous streams, play a strategic role as a historical axis for anthropogenic civilization, human welfare also habitat and migration pathway of commercial – biologic valuable fishes e.g. Caspian trout, Caspian kuttum, members of Cyprinidae family in south Caspian Sea drainage. Treats such as overfishing of Caspian trout and Red spotted trout stocks in mountainous headwaters, barriers construction and manipulations those are out of river carrying capacity developed by human activities, affected normal function of river as well. Sand mining big factories establishment next to the river, legal and illegal trade of river sediments, direct entry of Tonekabon landfill leakage into the river, development of Rainbow trout farms since 3 decades and huge effluents into the river containing dead fish and types of solids, escapement of cultured Rainbow trouts into the river, … are major minimum factors which needs basic information for integrating inclusively drainage management system. Cheshmehkileh River contains Headwaters of Dohezar (Daryasar & Nusha), Sehezar and Valamroud rivers during 13 monthly sampling phases between September 2009 and October 2010 based on macrozoobenthoses investigations by EPT, EPT/C EPA protocols, measurements of nominated physic-chemical and microbiologic parameters. Probability of Rainbow trouts escapement and invasion, existence, nutrition in Cheshmehkileh environment indeed investigated. Data analysis explained significant differences (P〈0.05) between groups of measured parameters in different sampling stations. Dendogram of clustered analysis based on consolidation of major biologic/ physic-chemical and microbiologic parameters, separated stations No. 1, 3, 2, 4 in one group and remained classified in different groups. Station 8 and 9 similarly separated which expressed general similarities according to Sehezar river environment which were differs in comparison with other stations. Station 11 separated according to its natural quality of water and environment. Similarities between station 10 to Sehezar river stations 8 and 9 expressed general influence of Sehezar River more than Dohezar River in Cheshmehkileh condition especially in station No. 10. High scores of EPT and EPT/C indices in upstream stations 1, 3 and 8 also low score of indices in stations 7, 13 and 6 expressed levels of environment quality between these groups of stations. Maximum average biomass of macroinvertebrates belongs to Trichoptera order in Cheshmehkileh River. Significant decrease of biomass in stations 11, 12 and 13 in comparison with other stations stated environment degradation in mentioned stations relevant to excessive sand mining as well. Pollution resistant groups of invertebrates significantly increased in downstreams against upstream stations. Also disappearing of Plecoptera order in station No. 7, 9, 10 and 13 stated low quality of environment in comparison with upstream stations. Confirmation of effects quality and quantity for point and non-point sources of imported pollutants require specific management considerations in order to present exploitations, pollutants control and emergencies for river monitoring in forthcoming years.
    Description: Iranian Fisheries Science Research Institute
    Description: Published
    Keywords: River ; Pollution ; Aquaculture ; EPTC ; Assessment ; Macroinvertebrates ; Chemistry ; Microbiology
    Repository Name: AquaDocs
    Type: Report , Refereed
    Format: 138pp.
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  • 4
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution September 2018
    Description: Many chemical constituents are removed from the ocean by attachment to settling particles, a process referred to as “scavenging.” Radioisotopes of thorium, a highly particle-reactive element, have been used extensively to study scavenging in the ocean. However, this process is complicated by the highly variable chemical composition and concentration of particles in oceanic waters. This thesis focuses on understanding the cycling of thorium as affected by particle concentration and particle composition in the North Atlantic. This objective is addressed using (i) the distributions 228,230,234Th, their radioactive parents, particle composition, and bulk particle concentration, as measured or estimated along the GEOTRACES North Atlantic Transect (GA03) and (ii) a model for the reversible exchange of thorium with particles. Model parameters are either estimated by inversion (chapter 2-4), or prescribed in order to simulate 230Th in a circulation model (chapter 5). The major findings of this thesis follow. In chapters 2 and 3, I find that the rate parameters of the reversible exchange model show systematic variations along GA03. In particular, 𝑘1, the apparent first-order rate "constant" of Th adsorption onto particles, generally presents maxima in the mesopelagic zone and minima below. A positive correlation between 𝑘1 and bulk particle concentration is found, consistent with the notion that the specific rate at which a metal in solution attaches to particles increases with the number of surface sites available for adsorption. In chapter 4, I show that Mn (oxyhydr)oxides and biogenic particles most strongly influence 𝑘1 west of the Mauritanian upwelling, but that biogenic particles dominate 𝑘1 in this region. In chapter 5, I find that dissolved 230Th data are best represented by a model that assumes enhanced values of 𝑘1 near the seafloor. Collectively, my findings suggest that spatial variations in Th radioisotope activities observed in the North Atlantic reflect at least partly variations in the rate at which Th is removed from the water column.
    Description: This work was supported by the US National Science Foundation. Two US NSF grants have supported the research in this thesis (OCE-1232578 and OCE-155644).
    Keywords: Thorium ; Chemistry
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 5
    Publication Date: 2021-05-19
    Description: Наряду с исследованиями по определению сырьевой базы Азово-Черноморского бассейна, при создании института АзЧерНИРО в 1933 г. была сразу организована научно-исследовательская лаборатория техники лова рыбы. За все время функционирования этого подразделения такие специалисты, как С.С. Виннов, О.И. Саковец, С.Я. Наместников, Е.Е. Шапунов, В.М. Кириллов, В.Г. Герасимов, В.С. Долбиш, Н.Г. Думин, В.Г. Васильев, А.А. Яковлев, Е.С. Деньгин, В.И. Абакаров, В.Н. Миронов, В.В. Стрельцов, А.С. Вайнерман, В.К. Яшкин, Ю.В. Шишов, А.М. Стафикопуло в течение многих лет вносили огромный вклад в развитие рыболовства в Азово-Черноморском бассейне и Мировом океане. До 1950 г. траловый промысел в Черном море отсутствовал, хотя были известны попытки внедрить этот вид лова в черноморское рыболовство. Так, в начале 1909 г. в северо-западной части Черного моря работал траулер «Федя». К концу 1911 г. количество траулеров, которые работали в данном регионе моря, увеличилось до 9 судов. Уловы состояли на 98-99 % из осетровых и на 1-2 % из камбалы. Ввиду очень большого вылова молоди осетровых рыб траловый промысел вскоре был запрещен. В 1932 г. из Мурманска для выяснения эффективности тралового лова в Черном море был послан рыболовный траулер «Абрек». Почти у всего черноморского побережья пробовали ловить отечественным промысловым тралом, применяемым в Баренцевом море для добычи трески. При этом отмечалось, что уловы камбалы были очень низкими. Очевидно, одной из причин была неприспособленность самой конструкции трала для лова этого вида рыб. В конце 1933 г. траулер вернулся в Мурманск. В 1949 г. Черноморская научно-промысловая экспедиция возобновила работы по освоению тралового лова в Черном море. Перед экспедицией стояла задача всесторонне изучить ихтиофауну моря и выяснить возможности применения ряда поисковых орудий лова, в том числе донного трала. С этой целью было разработано и испытано несколько типов донных тралов. С конца 1949 г. были начаты исследования по разработке конструкции разноглубинного трала для Черного моря. К тому времени инженерами М.К. Кокоревым, В.Ф. Шушпановым и А.Н. Потехиным была разработана специальная подъемно-распорная система. В соответствии с ее техническими данными в дальнейшем проектировались сетные части трала. Первый проект опытного рыболовного разноглубинного морского трала разрабатывался для лова мелких черноморских пелагических рыб в толще воды, на глубинах от 0 до 100 м, с одного судна. Большой вклад в развитие тралового промысла в Черном море внес А.Н. Самарянов.
    Description: Published
    Keywords: Engineering ; Fishing gear ; Fishing fleet ; Fishing vessels ; Trawlers ; Anchovy fisheries ; Sprat fisheries ; Purse fishing ; Commercial species ; Mullets
    Repository Name: AquaDocs
    Type: Conference Material , Non Refereed
    Format: pp.247-254
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  • 6
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-02-16
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 7
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-02-16
    Description: The comment and response concerning the report of oxidation of methane to methanol by water (Reports, 5 May 2017, p. 523) do not fully capture the implications of thermodynamic limitations. A nonisothermal process in which each cycle requires a large temperature swing and permits only substoichiometric methane conversion surely could not be carried out on any practical scale.
    Keywords: Chemistry
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 8
    Publication Date: 2018-02-16
    Description: Labinger argues that stepwise reaction of methane with water to produce methanol and hydrogen will never be commercially feasible because of its substoichiometric basis with respect to the active site and the requirement of a large temperature swing. This comment is not touching any new ground, beyond describing the thermodynamic feasibility, thermal cycling, and the role of water as discussed previously. Most important, it does not have a solid numerical basis.
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 9
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-27
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 10
    Publication Date: 2018-07-27
    Description: Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium–weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond–forming reactions, including carbon-hydrogen (C–H) insertion into unactivated sp 3 C–H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C–H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.
    Keywords: Chemistry
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  • 11
    Publication Date: 2018-06-22
    Description: It is commonly assumed that recognition and discrimination of chirality, both in nature and in artificial systems, depend solely on spatial effects. However, recent studies have suggested that charge redistribution in chiral molecules manifests an enantiospecific preference in electron spin orientation. We therefore reasoned that the induced spin polarization may affect enantiorecognition through exchange interactions. Here we show experimentally that the interaction of chiral molecules with a perpendicularly magnetized substrate is enantiospecific. Thus, one enantiomer adsorbs preferentially when the magnetic dipole is pointing up, whereas the other adsorbs faster for the opposite alignment of the magnetization. The interaction is not controlled by the magnetic field per se, but rather by the electron spin orientations, and opens prospects for a distinct approach to enantiomeric separations.
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 12
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-06-29
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 13
    Publication Date: 2018-12-14
    Description: Theory has established the importance of geometric phase (GP) effects in the adiabatic dynamics of molecular systems with a conical intersection connecting the ground- and excited-state potential energy surfaces, but direct observation of their manifestation in chemical reactions remains a major challenge. Here, we report a high-resolution crossed molecular beams study of the H + HD -〉 H 2 + D reaction at a collision energy slightly above the conical intersection. Velocity map ion imaging revealed fast angular oscillations in product quantum state–resolved differential cross sections in the forward scattering direction for H 2 products at specific rovibrational levels. The experimental results agree with adiabatic quantum dynamical calculations only when the GP effect is included.
    Keywords: Chemistry
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  • 14
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-17
    Keywords: Chemistry
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    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 15
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-17
    Keywords: Chemistry
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    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 16
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-17
    Description: The chemistry of the carbonyl group is essential to modern organic synthesis. The preparation of substituted, enantioenriched 1,3- or 1,5-dicarbonyls is well developed, as their disconnection naturally follows from the intrinsic polarity of the carbonyl group. By contrast, a general enantioselective access to quaternary stereocenters in acyclic 1,4-dicarbonyl systems remains an unresolved problem, despite the tremendous importance of 2,3-substituted 1,4-dicarbonyl motifs in natural products and drug scaffolds. Here we present a broad enantioselective and stereodivergent strategy to access acyclic, polysubstituted 1,4-dicarbonyls via acid-catalyzed [3,3]-sulfonium rearrangement starting from vinyl sulfoxides and ynamides. The stereochemistry at sulfur governs the absolute sense of chiral induction, whereas the double bond geometry dictates the relative configuration of the final products.
    Keywords: Chemistry
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  • 17
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-17
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 18
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-17
    Keywords: Engineering
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 19
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-17
    Description: Polyamide thickness and roughness have been identified as critical properties that affect thin-film composite membrane performance for reverse osmosis. Conventional formation methodologies lack the ability to control these properties independently with high resolution or precision. An additive approach is presented that uses electrospraying to deposit monomers directly onto a substrate, where they react to form polyamide. The small droplet size coupled with low monomer concentrations result in polyamide films that are smoother and thinner than conventional polyamides, while the additive nature of the approach allows for control of thickness and roughness. Polyamide films are formed with a thickness that is controllable down to 4-nanometer increments and a roughness as low as 2 nanometers while still exhibiting good permselectivity relative to a commercial benchmarking membrane.
    Keywords: Engineering
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  • 20
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-17
    Description: With the recent soaring production of natural gas, the use of methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report the development of photocatalytic C–H amination, alkylation, and arylation of methane, ethane, and higher alkanes under visible light irradiation at ambient temperature. High catalytic efficiency (turnover numbers up to 2900 for methane and 9700 for ethane) and selectivity were achieved using abundant, inexpensive cerium salts as photocatalysts. Ligand-to-metal charge transfer excitation generated alkoxy radicals from simple alcohols that in turn acted as hydrogen atom transfer catalysts. The mixed-phase gas/liquid reaction was adapted to continuous flow, enabling the efficient use of gaseous feedstocks in scalable photocatalytic transformations.
    Keywords: Chemistry
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  • 21
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-24
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 22
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-24
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 23
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-31
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 24
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-31
    Description: Intrigued by the potential of nanoscale machines, scientists have long attempted to control molecular motion. We monitored the individual 0.7-nanometer steps of a single molecular hopper as it moved in an electric field along a track in a nanopore controlled by a chemical ratchet. The hopper demonstrated characteristics desired in a moving molecule: defined start and end points, processivity, no chemical fuel requirement, directional motion, and external control. The hopper was readily functionalized to carry cargos. For example, a DNA molecule could be ratcheted along the track in either direction, a prerequisite for nanopore sequencing.
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 25
    Publication Date: 2018-09-07
    Description: Zeolitic imidazolate framework (ZIF) membranes are emerging as a promising energy-efficient separation technology. However, their reliable and scalable manufacturing remains a challenge. We demonstrate the fabrication of ZIF nanocomposite membranes by means of an all-vapor-phase processing method based on atomic layer deposition (ALD) of ZnO in a porous support followed by ligand-vapor treatment. After ALD, the obtained nanocomposite exhibits low flux and is not selective, whereas after ligand-vapor (2-methylimidazole) treatment, it is partially transformed to ZIF and shows stable performance with high mixture separation factor for propylene over propane (an energy-intensive high-volume separation) and high propylene flux. Membrane synthesis through ligand-induced permselectivation of a nonselective and impermeable deposit is shown to be simple and highly reproducible and holds promise for scalability.
    Keywords: Engineering
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  • 26
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-09-14
    Keywords: Engineering
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 27
    Publication Date: 2018-09-14
    Description: Insects are among the most agile natural flyers. Hypotheses on their flight control cannot always be validated by experiments with animals or tethered robots. To this end, we developed a programmable and agile autonomous free-flying robot controlled through bio-inspired motion changes of its flapping wings. Despite being 55 times the size of a fruit fly, the robot can accurately mimic the rapid escape maneuvers of flies, including a correcting yaw rotation toward the escape heading. Because the robot’s yaw control was turned off, we showed that these yaw rotations result from passive, translation-induced aerodynamic coupling between the yaw torque and the roll and pitch torques produced throughout the maneuver. The robot enables new methods for studying animal flight, and its flight characteristics allow for real-world flight missions.
    Keywords: Engineering
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  • 28
    Publication Date: 2018-09-21
    Description: Phosphorothioate nucleotides have emerged as powerful pharmacological substitutes of their native phosphodiester analogs with important translational applications in antisense oligonucleotide (ASO) therapeutics and cyclic dinucleotide (CDN) synthesis. Stereocontrolled installation of this chiral motif has long been hampered by the systemic use of phosphorus(III) [P(III)]–based reagent systems as the sole practical means of oligonucleotide assembly. A fundamentally different approach is described herein: the invention of a P(V)-based reagent platform for programmable, traceless, diastereoselective phosphorus-sulfur incorporation. The power of this reagent system is demonstrated through the robust and stereocontrolled synthesis of various nucleotidic architectures, including ASOs and CDNs, via an efficient, inexpensive, and operationally simple protocol.
    Keywords: Chemistry
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  • 29
    Publication Date: 2018-09-21
    Description: Here we report an anomalous porous molecular crystal built of C–H···N-bonded double-layered roof-floor components and wall components of a segregatively interdigitated architecture. This complicated porous structure consists of only one type of fully aromatic multijoint molecule carrying three identical dipyridylphenyl wedges. Despite its high symmetry, this molecule accomplishes difficult tasks by using two of its three wedges for roof-floor formation and using its other wedge for wall formation. Although a C–H···N bond is extremely labile, the porous crystal maintains its porosity until thermal breakdown of the C–H···N bonds at 202°C occurs, affording a nonporous polymorph. Though this nonporous crystal survives even at 325°C, it can retrieve the parent porosity under acetonitrile vapor. These findings show how one can translate simplicity into ultrahigh complexity.
    Keywords: Chemistry
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  • 30
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-09-28
    Keywords: Chemistry
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  • 31
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-09-28
    Keywords: Chemistry
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  • 32
    Publication Date: 2018-09-28
    Description: Some of the simplest and most powerful carbon-carbon bond forming strategies take advantage of readily accessible ubiquitous motifs: carbonyls and olefins. Here we report a fundamentally distinct mode of reactivity between carbonyls and olefins that differs from established acid-catalyzed carbonyl-ene, Prins, and carbonyl-olefin metathesis reaction paths. A range of epsilon, zeta-unsaturated ketones undergo Brønsted acid–catalyzed intramolecular cyclization to provide tetrahydrofluorene products via the formation of two new carbon-carbon bonds. Theoretical calculations and accompanying mechanistic studies suggest that this carbocyclization reaction proceeds through the intermediacy of a transient oxetane formed by oxygen atom transfer. The complex polycyclic frameworks in this product class appear as common substructures in organic materials, bioactive natural products, and recently developed pharmaceuticals.
    Keywords: Chemistry
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  • 33
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-09-28
    Description: Alkene aminoarylation with a single, bifunctional reagent is a concise synthetic strategy. We report a catalytic protocol for the addition of arylsulfonylacetamides across electron-rich alkenes with complete anti-Markovnikov regioselectivity and excellent diastereoselectivity to provide 2,2-diarylethylamines. In this process, single-electron alkene oxidation enables carbon-nitrogen bond formation to provide a key benzylic radical poised for a Smiles-Truce 1,5-aryl shift. This reaction is redox-neutral, exhibits broad functional group compatibility, and occurs at room temperature with loss of sulfur dioxide. As this process is driven by visible light, uses readily available starting materials, and demonstrates convergent synthesis, it is well suited for use in a variety of synthetic endeavors.
    Keywords: Chemistry
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  • 34
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-05
    Keywords: Chemistry
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  • 35
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-05
    Keywords: Chemistry
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  • 36
    Publication Date: 2018-10-05
    Description: Photocatalysis based on optically active, "plasmonic" metal nanoparticles has emerged as a promising approach to facilitate light-driven chemical conversions under far milder conditions than thermal catalysis. However, an understanding of the relation between thermal and electronic excitations has been lacking. We report the substantial light-induced reduction of the thermal activation barrier for ammonia decomposition on a plasmonic photocatalyst. We introduce the concept of a light-dependent activation barrier to account for the effect of light illumination on electronic and thermal excitations in a single unified picture. This framework provides insight into the specific role of hot carriers in plasmon-mediated photochemistry, which is critically important for designing energy-efficient plasmonic photocatalysts.
    Keywords: Chemistry
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  • 37
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-12
    Keywords: Chemistry
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  • 38
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-12
    Keywords: Chemistry
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  • 39
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-12
    Description: Single-electron reduction of a carbonyl to a ketyl enables access to a polarity-reversed platform of reactivity for this cornerstone functional group. However, the synthetic utility of the ketyl radical is hindered by the strong reductants necessary for its generation, which also limit its reactivity to net reductive mechanisms. We report a strategy for net redox-neutral generation and reaction of ketyl radicals. The in situ conversion of aldehydes to α-acetoxy iodides lowers their reduction potential by more than 1 volt, allowing for milder access to the corresponding ketyl radicals and an oxidative termination event. Upon subjecting these iodides to a dimanganese decacarbonyl precatalyst and visible light irradiation, an atom transfer radical addition (ATRA) mechanism affords a broad scope of vinyl iodide products with high Z -selectivity.
    Keywords: Chemistry
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  • 40
    Publication Date: 2018-10-12
    Description: Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert -butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.
    Keywords: Chemistry
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  • 41
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-12-21
    Keywords: Chemistry
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  • 42
    Publication Date: 2018-12-21
    Description: Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation [(Cp i Pr5 )Dy(Cp*)] + (Cp i Pr5 , penta-iso-propylcyclopentadienyl; Cp *, pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of U eff = 1541 wave number is also measured. The magnetic blocking temperature of T B = 80 kelvin for this cation overcomes an essential barrier toward the development of nanomagnet devices that function at practical temperatures.
    Keywords: Chemistry
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  • 43
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-19
    Keywords: Chemistry
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  • 44
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-19
    Description: The development of highly reactive and stereoselective catalytic systems is required not only to improve existing synthetic methods but also to invent distinct chemical reactions. Herein, a homogenized combination of nickel-based Lewis acid–surfactant-combined catalysts and single-walled carbon nanotubes is shown to exhibit substantial activity in water. In addition to the enhanced reactivity, stereoselective performance and long-term stability were demonstrated in asymmetric conjugate addition reactions of aldoximes to furnish chiral nitrones in high yields with excellent selectivities. The practical and straightforward application of the designed catalysts in water provides an expedient, environmentally benign, and highly efficient pathway to access optically active compounds.
    Keywords: Chemistry
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  • 45
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-11-02
    Keywords: Chemistry
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  • 46
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-12-14
    Keywords: Chemistry
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  • 47
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-10-26
    Keywords: Chemistry
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  • 48
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-11-02
    Description: Exploration of intermediates that enable chemoselective cycloaddition reactions and expeditious construction of fused- or bridged-ring systems is a continuous challenge for organic synthesis. As an intermediate of interest, the oxyallyl cation has been harnessed to synthesize architectures containing seven-membered rings via (4+3) cycloaddition. However, its potential to access five-membered skeletons is underdeveloped, largely due to the thermally forbidden (3+2) pathway. Here, the combination of a tailored precursor and a Pd(0) catalyst generates a Pd-oxyallyl intermediate that cyclizes with conjugated dienes to produce a diverse array of tetrahydrofuran skeletons. The cycloaddition overrides conventional (4+3) selectivity by proceeding through a stepwise pathway involving a Pd-allyl transfer and ring closure sequence. Subsequent treatment of the (3+2) adducts with a palladium catalyst converts the heterocycles to the carbocyclic cyclopentanones.
    Keywords: Chemistry
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  • 49
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-11-16
    Keywords: Chemistry
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  • 50
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-10
    Keywords: Chemistry
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  • 51
    Publication Date: 2018-08-10
    Description: Understanding the practical limitations of chemical reactions is critically important for efficiently planning the synthesis of compounds in pharmaceutical, agrochemical, and specialty chemical research and development. However, literature reports of the scope of new reactions are often cursory and biased toward successful results, severely limiting the ability to predict reaction outcomes for untested substrates. We herein illustrate strategies for carrying out large-scale surveys of chemical reactivity by using a material-sparing nanomole-scale automated synthesis platform with greatly expanded synthetic scope combined with ultrahigh-throughput matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry (MALDI-TOF MS).
    Keywords: Chemistry
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  • 52
    Publication Date: 2018-08-24
    Description: Researchers around the world have observed the formation of molecularly ordered structures of unknown origin on the surface of titanium dioxide (TiO 2 ) photocatalysts exposed to air and solution. Using a combination of atomic-scale microscopy and spectroscopy, we show that TiO 2 selectively adsorbs atmospheric carboxylic acids that are typically present in parts-per-billion concentrations while effectively repelling other adsorbates, such as alcohols, that are present in much higher concentrations. The high affinity of the surface for carboxylic acids is attributed to their bidentate binding. These self-assembled monolayers have the unusual property of being both hydrophobic and highly water-soluble, which may contribute to the self-cleaning properties of TiO 2 . This finding is relevant to TiO 2 photocatalysis, because the self-assembled carboxylate monolayers block the undercoordinated surface cation sites typically implicated in photocatalysis.
    Keywords: Chemistry
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  • 53
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-31
    Keywords: Chemistry
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  • 54
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-08-31
    Keywords: Chemistry
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  • 55
    Publication Date: 2018-08-31
    Description: The alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) typically engage in chemical bonding as classical main-group elements through their n s and n p valence orbitals, where n is the principal quantum number. Here we report the isolation and spectroscopic characterization of eight-coordinate carbonyl complexes M(CO) 8 (where M = Ca, Sr, or Ba) in a low-temperature neon matrix. Analysis of the electronic structure of these cubic O h -symmetric complexes reveals that the metal–carbon monoxide (CO) bonds arise mainly from [M(d )] -〉 (CO) 8 backdonation, which explains the strong observed red shift of the C-O stretching frequencies. The corresponding radical cation complexes were also prepared in gas phase and characterized by mass-selected infrared photodissociation spectroscopy, confirming adherence to the 18-electron rule more conventionally associated with transition metal chemistry.
    Keywords: Chemistry
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  • 56
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-09-07
    Keywords: Chemistry
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  • 57
    Publication Date: 2018-09-07
    Description: Mystery surrounds the transition from gas-phase hydrocarbon precursors to terrestrial soot and interstellar dust, which are carbonaceous particles formed under similar conditions. Although polycyclic aromatic hydrocarbons (PAHs) are known precursors to high-temperature carbonaceous-particle formation, the molecular pathways that initiate particle formation are unknown. We present experimental and theoretical evidence for rapid molecular clustering–reaction pathways involving radicals with extended conjugation. These radicals react with other hydrocarbon species to form covalently bound complexes that promote further growth and clustering by regenerating resonance-stabilized radicals through low-barrier hydrogen-abstraction and hydrogen-ejection reactions. Such radical–chain reaction pathways may lead to covalently bound clusters of PAHs and other hydrocarbons that would otherwise be too small to condense at high temperatures, thus providing the key mechanistic steps for rapid particle formation and surface growth by hydrocarbon chemisorption.
    Keywords: Chemistry
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  • 58
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-09-14
    Keywords: Chemistry
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  • 59
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-04-27
    Keywords: Chemistry
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  • 60
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-04-27
    Keywords: Chemistry
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  • 61
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-04-27
    Keywords: Engineering
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  • 62
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-04-27
    Description: Basic heteroarenes are a ubiquitous feature of pharmaceuticals and bioactive molecules, and Minisci-type additions of radical nucleophiles are a leading method for their elaboration. Despite many Minisci-type protocols that result in the formation of stereocenters, exerting control over the absolute stereochemistry at these centers remains an unmet challenge. We report a process for addition of prochiral radicals, generated from amino acid derivatives, to pyridines and quinolines. Our method offers excellent control of both enantioselectivity and regioselectivity. An enantiopure chiral Brønsted acid catalyst serves both to activate the substrate and induce asymmetry, while an iridium photocatalyst mediates the required electron transfer processes. We anticipate that this method will expedite access to enantioenriched small-molecule building blocks bearing versatile basic heterocycles.
    Keywords: Chemistry
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  • 63
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-05-25
    Keywords: Chemistry
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  • 64
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-05-25
    Keywords: Chemistry
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  • 65
    Publication Date: 2018-10-26
    Description: Primary amines are essential constituents of biologically active molecules and versatile intermediates in the synthesis of drugs and agrochemicals. However, their preparation from easily accessible alkenes remains challenging. Here, we report a general strategy to access primary amines from alkenes through an operationally simple iron-catalyzed aminochlorination reaction. A stable hydroxylamine derivative and benign sodium chloride act as the respective nitrogen and chlorine sources. The reaction proceeds at room temperature under air; tolerates a large scope of aliphatic and conjugated alkenes, including densely functionalized substrates; and provides excellent anti-Markovnikov regioselectivity with respect to the amino group. The reactivity of the 2-chloroalkylamine products, an understudied class of amphoteric molecules, enables facile access to linear or branched aliphatic amines, aziridines, aminonitriles, azido amines, and homoallylic amines.
    Keywords: Chemistry
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  • 66
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-11-09
    Keywords: Chemistry
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  • 67
    Publication Date: 2018-11-09
    Description: Despite the enormous potential for the use of stereospecific cross-coupling reactions to rationally manipulate the three-dimensional structure of organic molecules, the factors that control the transfer of stereochemistry in these reactions remain poorly understood. Here we report a mechanistic and synthetic investigation into the use of enantioenriched alkylboron nucleophiles in stereospecific Pd-catalyzed Suzuki cross-coupling reactions. By developing a suite of molecular descriptors of phosphine ligands, we could apply predictive statistical models to select or design distinct ligands that respectively promoted stereoinvertive and stereoretentive cross-coupling reactions. Stereodefined branched structures were thereby accessed through the predictable manipulation of absolute stereochemistry, and a general model for the mechanism of alkylboron transmetallation was proposed.
    Keywords: Chemistry
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  • 68
    Publication Date: 2018-11-16
    Description: Heterobiaryls composed of pyridine and diazine rings are key components of pharmaceuticals and are often central to pharmacological function. We present an alternative approach to metal-catalyzed cross-coupling to make heterobiaryls using contractive phosphorus C–C couplings, also termed phosphorus ligand coupling reactions. The process starts by regioselective phosphorus substitution of the C–H bonds para to nitrogen in two successive heterocycles; ligand coupling is then triggered via acidic alcohol solutions to form the heterobiaryl bond. Mechanistic studies imply that ligand coupling is an asynchronous process involving migration of one heterocycle to the ipso position of the other around a central pentacoordinate P(V) atom. The strategy can be applied to complex drug-like molecules containing multiple reactive sites and polar functional groups, and also enables convergent coupling of drug fragments and late-stage heteroarylation of pharmaceuticals.
    Keywords: Chemistry
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  • 69
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-06
    Keywords: Chemistry
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  • 70
    Publication Date: 2018-07-06
    Description: Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF 3 I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF 3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.
    Keywords: Chemistry
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  • 71
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-13
    Keywords: Chemistry
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  • 72
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-06-22
    Keywords: Chemistry
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  • 73
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-04-13
    Keywords: Chemistry
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  • 74
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-05-04
    Keywords: Chemistry
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  • 75
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-05-11
    Keywords: Chemistry
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  • 76
    Publication Date: 2018-05-11
    Description: Common anionic nucleophiles such as those derived from inorganic salts have not been used for enantioselective catalysis because of their insolubility. Here, we report that merging hydrogen bonding and phase-transfer catalysis provides an effective mode of activation for nucleophiles that are insoluble in organic solvents. This catalytic manifold relies on hydrogen bonding complexation to render nucleophiles soluble and reactive, while simultaneously inducing asymmetry in the ensuing transformation. We demonstrate the concept using a chiral bis-urea catalyst to form a tridentate hydrogen bonding complex with fluoride from its cesium salt, thereby enabling highly efficient enantioselective ring opening of episulfonium ion. This fluorination method is synthetically valuable considering the scarcity of alternative protocols and points the way to wider application of the catalytic approach with diverse anionic nucleophiles.
    Keywords: Chemistry
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  • 77
    Publication Date: 2018-05-18
    Description: Carbon dioxide (CO 2 ) electroreduction could provide a useful source of ethylene, but low conversion efficiency, low production rates, and low catalyst stability limit current systems. Here we report that a copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO 2 to ethylene with 70% faradaic efficiency at a potential of –0.55 volts versus a reversible hydrogen electrode (RHE). Hydroxide ions on or near the copper surface lower the CO 2 reduction and carbon monoxide (CO)–CO coupling activation energy barriers; as a result, onset of ethylene evolution at –0.165 volts versus an RHE in 10 molar potassium hydroxide occurs almost simultaneously with CO production. Operational stability was enhanced via the introduction of a polymer-based gas diffusion layer that sandwiches the reaction interface between separate hydrophobic and conductive supports, providing constant ethylene selectivity for an initial 150 operating hours.
    Keywords: Chemistry
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  • 78
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-05-25
    Keywords: Chemistry
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  • 79
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-03-23
    Description: White phosphorus, generated in the legacy thermal process for phosphate rock upgrading, has long been the key industrial intermediate for the synthesis of phosphorus-containing chemicals, including herbicides, flame-retardants, catalyst ligands, battery electrolytes, pharmaceuticals, and detergents. In contrast, phosphate fertilizers are made on a much larger scale from phosphoric acid, obtained by treating phosphate rock with sulfuric acid. Dehydration of phosphoric acid using sodium chloride gives trimetaphosphate, and here we report that trichlorosilane, primarily used for the production of high-purity silicon, reduces trimetaphosphate to the previously unknown bis(trichlorosilyl)phosphide anion. This anion offers an entry point to value-added organophosphorus chemicals such as primary and secondary alkyl phosphines, and thus to organophosphinates, and can also be used to prepare phosphine gas and the hexafluorophosphate anion, all previously available only downstream from white phosphorus.
    Keywords: Chemistry
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  • 80
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-04-06
    Keywords: Chemistry
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  • 81
    Publication Date: 2018-04-06
    Description: Cross-coupling chemistry is widely applied to carbon-carbon bond formation in the synthesis of medicines, agrochemicals, and other functional materials. Recently, single-electron–induced variants of this reaction class have proven particularly useful in the formation of C(sp 2 )–C(sp 3 ) linkages, although certain compound classes have remained a challenge. Here, we report the use of sulfones to activate the alkyl coupling partner in nickel-catalyzed radical cross-coupling with aryl zinc reagents. This method’s tolerance of fluoroalkyl substituents proved particularly advantageous for the streamlined preparation of pharmaceutically oriented fluorinated scaffolds that previously required multiple steps, toxic reagents, and nonmodular retrosynthetic blueprints. Five specific sulfone reagents facilitate the rapid assembly of a vast set of compounds, many of which contain challenging fluorination patterns.
    Keywords: Chemistry
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  • 82
    Publication Date: 2018-05-04
    Description: Plasmon-induced chemical reactions of molecules adsorbed on metal nanostructures are attracting increased attention for photocatalytic reactions. However, the mechanism remains controversial because of the difficulty of direct observation of the chemical reactions in the plasmonic field, which is strongly localized near the metal surface. We used a scanning tunneling microscope (STM) to achieve real-space and real-time observation of a plasmon-induced chemical reaction at the single-molecule level. A single dimethyl disulfide molecule on silver and copper surfaces was dissociated by the optically excited plasmon at the STM junction. The STM study combined with theoretical calculations shows that this plasmon-induced chemical reaction occurred by a direct intramolecular excitation mechanism.
    Keywords: Chemistry
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  • 83
    Publication Date: 2018-05-25
    Description: Identifying catalyst activation modes that exploit one-electron chemistry and overcome associated deactivation pathways will be transformative for developing first-row transition metal catalysts with performance equal or, ideally, superior to precious metals. Here we describe a zinc-activation method compatible with high-throughput reaction discovery that identified scores of cobalt-phosphine combinations for the asymmetric hydrogenation of functionalized alkenes. An optimized catalyst prepared from ( R , R )-Ph-BPE {Ph-BPE, 1,2-bis[(2 R ,5 R )-2,5-diphenylphospholano]ethane} and cobalt chloride [CoCl 2 ·6H 2 O] exhibited high activity and enantioselectivity in protic media and enabled the asymmetric synthesis of the epilepsy medication levetiracetam at 200-gram scale with 0.08 mole % catalyst loading. Stoichiometric studies established that the cobalt (II) catalyst precursor ( R , R )-Ph-BPECoCl 2 underwent ligand displacement by methanol, and zinc promoted facile one-electron reduction to cobalt (I), which more stably bound the phosphine.
    Keywords: Chemistry
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  • 84
    Publication Date: 2018-06-01
    Description: Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.
    Keywords: Chemistry
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  • 85
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-05-18
    Keywords: Chemistry
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  • 86
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-06-01
    Keywords: Chemistry
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  • 87
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-03-23
    Keywords: Chemistry
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  • 88
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-03-23
    Keywords: Chemistry
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  • 89
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-03-30
    Keywords: Chemistry
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  • 90
    Publication Date: 2018-03-30
    Description: The activation of olefins for asymmetric chemical synthesis traditionally relies on transition metal catalysts. In contrast, biological enzymes with Brønsted acidic sites of appropriate strength can protonate olefins and thereby generate carbocations that ultimately react to form natural products. Although chemists have recently designed chiral Brønsted acid catalysts to activate imines and carbonyl compounds, mimicking these enzymes to protonate simple olefins that then engage in asymmetric catalytic reactions has remained a substantial synthetic challenge. Here, we show that a class of confined and strong chiral Brønsted acids enables the catalytic asymmetric intramolecular hydroalkoxylation of unbiased olefins. The methodology gives rapid access to biologically active 1,1-disubstituted tetrahydrofurans, including (–)-Boivinianin A.
    Keywords: Chemistry
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  • 91
    Publication Date: 2018-04-13
    Description: Machine learning methods are becoming integral to scientific inquiry in numerous disciplines. We demonstrated that machine learning can be used to predict the performance of a synthetic reaction in multidimensional chemical space using data obtained via high-throughput experimentation. We created scripts to compute and extract atomic, molecular, and vibrational descriptors for the components of a palladium-catalyzed Buchwald-Hartwig cross-coupling of aryl halides with 4-methylaniline in the presence of various potentially inhibitory additives. Using these descriptors as inputs and reaction yield as output, we showed that a random forest algorithm provides significantly improved predictive performance over linear regression analysis. The random forest model was also successfully applied to sparse training sets and out-of-sample prediction, suggesting its value in facilitating adoption of synthetic methodology.
    Keywords: Chemistry
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  • 92
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-06-22
    Keywords: Chemistry
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  • 93
    Publication Date: 2018-06-29
    Description: Chiral amines are widely used as catalysts in asymmetric synthesis to activate carbonyl groups for α-functionalization. Carbonyl catalysis reverses that strategy by using a carbonyl group to activate a primary amine. Inspired by biological carbonyl catalysis, which is exemplified by reactions of pyridoxal-dependent enzymes, we developed an N-quaternized pyridoxal catalyst for the asymmetric Mannich reaction of glycinate with aryl N -diphenylphosphinyl imines. The catalyst exhibits high activity and stereoselectivity, likely enabled by enzyme-like cooperative bifunctional activation of the substrates. Our work demonstrates the catalytic utility of the pyridoxal moiety in asymmetric catalysis.
    Keywords: Chemistry
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  • 94
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-13
    Keywords: Chemistry
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  • 95
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-13
    Description: Deconstructive functionalizations involving scission of carbon-carbon double bonds are well established. In contrast, unstrained C(sp 3 )–C(sp 3 ) bond cleavage and functionalization have less precedent. Here we report the use of deconstructive fluorination to access mono- and difluorinated amine derivatives by C(sp 3 )–C(sp 3 ) bond cleavage in saturated nitrogen heterocycles such as piperidines and pyrrolidines. Silver-mediated ring-opening fluorination using Selectfluor highlights a strategy for cyclic amine functionalization and late-stage skeletal diversification, establishing cyclic amines as synthons for amino alkyl radicals and providing synthetic routes to valuable building blocks.
    Keywords: Chemistry
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  • 96
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-20
    Keywords: Chemistry
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  • 97
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-06
    Keywords: Chemistry
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  • 98
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-06
    Description: Transformation of simple precursors into structurally complex cyclobutanes, present in many biologically important natural products and pharmaceuticals, is of considerable interest in medicinal chemistry. Starting from 1,3-enynes and ethylene, both exceptionally inexpensive starting materials, we report a cobalt-catalyzed route to vinylcyclobutenes, as well as the further enantioselective addition of ethylene to these products to form complex cyclobutanes with all-carbon quaternary centers. These reactions can proceed in discrete stages or in a tandem fashion to achieve three highly selective carbon-carbon bond formations in one pot using a single chiral cobalt catalyst.
    Keywords: Chemistry
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  • 99
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2018-07-27
    Keywords: Chemistry
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  • 100
    Publication Date: 2018-02-23
    Description: Currently, the only compounds known to support fixation and functionalization of dinitrogen (N 2 ) under nonmatrix conditions are based on metals. Here we present the observation of N 2 binding and reduction by a nonmetal, specifically a dicoordinate borylene. Depending on the reaction conditions under which potassium graphite is introduced as a reductant, N 2 binding to two borylene units results in either neutral (B 2 N 2 ) or dianionic ([B 2 N 2 ] 2– ) products that can be interconverted by respective exposure to further reductant or to air. The 15 N isotopologues of the neutral and dianionic molecules were prepared with 15 N-labeled dinitrogen, allowing observation of the nitrogen nuclei by 15 N nuclear magnetic resonance spectroscopy. Protonation of the dianionic compound with distilled water furnishes a diradical product with a central hydrazido B 2 N 2 H 2 unit. All three products were characterized spectroscopically and crystallographically.
    Keywords: Chemistry
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