Publication Date:
2016-04-21
Description:
New methods and strategies for the direct functionalization of C-H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as "classics". Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C-H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabling the adoption of this C-H oxidation strategy in large-scale industrial settings without substantial environmental impact.〈br /〉〈br /〉〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4860034/" target="_blank"〉〈img src="https://static.pubmed.gov/portal/portal3rc.fcgi/4089621/img/3977009" border="0"〉〈/a〉 〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4860034/" target="_blank"〉This paper as free author manuscript - peer-reviewed and accepted for publication〈/a〉〈br /〉〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Horn, Evan J -- Rosen, Brandon R -- Chen, Yong -- Tang, Jiaze -- Chen, Ke -- Eastgate, Martin D -- Baran, Phil S -- GM-097444/GM/NIGMS NIH HHS/ -- R01 GM073949/GM/NIGMS NIH HHS/ -- R01 GM097444/GM/NIGMS NIH HHS/ -- England -- Nature. 2016 May 5;533(7601):77-81. doi: 10.1038/nature17431. Epub 2016 Apr 20.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, The Scripps Research Institute, La Jolla, California 92037, USA. ; Asymchem Life Science (Tianjin), Tianjin Economic-Technological Development Zone, Tianjin 300457, China. ; Chemical Development, Bristol-Myers Squibb, New Brunswick, New Jersey 08903, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/27096371" target="_blank"〉PubMed〈/a〉
Keywords:
Allyl Compounds/chemistry
;
Biological Products/chemical synthesis/chemistry
;
Carbon/*chemistry
;
*Chemistry Techniques, Synthetic
;
Electrochemistry
;
Green Chemistry Technology
;
Hydrogen/*chemistry
;
Oxidants/*chemistry
;
Oxidation-Reduction
;
Substrate Specificity
Print ISSN:
0028-0836
Electronic ISSN:
1476-4687
Topics:
Biology
,
Chemistry and Pharmacology
,
Medicine
,
Natural Sciences in General
,
Physics
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