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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 29 (1990), S. 1320-1367 
    ISSN: 0570-0833
    Keywords: Synthetic methods ; Future of chemistry ; Chemistry today ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This review article is an attempt to sketch the important developments in organic synthesis during the past 25 years, and to project them into the future. - The primary motivations that once induced chemists to undertake natural product syntheses no longer exist. Instead of target structures themselves, molecular function and activity now occupy center stage. Thus, inhibitors with an affinity for all the important natural enzymes and receptors have moved to the fore as potential synthetic targets. - New synthetic methods are most likely to be encountered in the fields of biological and organometallic chemistry. Enzymes, whole organisms, and cell cultures for enan-tioselective synthesis of specific substances have already been incorporated into the synthetic arsenals of both research laboratories and industry. In addition, designing appropriate analogues to transition states and intermediates should soon make it possible, with the aid of the mammalian immune system and gene technology, to prepare catalytically active monoclonal antibodies for almost any reaction; perhaps, more important, such processes will increasingly come to be applied on an industrial scale.-The discovery of truly new reactions is likely to be limited to the realm of transition-metal organic chemistry, which will almost certainly provide us with additional “miracle reagents” in the years to come. As regards main group elements (“organoelemental chemistry”), we can surely anticipate further stepwise improvements in experimental procedures and the broader application of special techniques, leading to undreamed of efficiency and selectivity with respect to known procedures. The primary center of attention for all synthetic methods will continue to shift toward catalytic and enantioselective variants; indeed, it will not be long before such modifications will be available with every standard reaction for converting achiral educts into chiral products. Analysis, spectroscopy, structure determination, theory, and electronic data processing have all become indispensable in organic synthesis. Only with the aid of these “tools” will the methods of organic chemistry permit selective syntheses of ever larger and more complex systems on both the molecular and supramolecular levels. - Examples have been introduced throughout this discourse to illustrate its many themes, and a very comprehensive bibliography should help the interested reader become more familiar with important keywords and authors.[The list of references is also available upon request in the form of a Microsoft Word© file on diskette.] - This article will have served its intended purpose if it changes the minds of some of those who claim organic chemistry is a mature science, and if it causes students to discover the vitality and forcefulness with which organic synthesis is meeting new challenges and attempting to fulfill old dreams.Er zeigt uns so in seinem wissenschaftlichen Leben, daß die Chemie nicht von einer Theorie, nicht von einer Methode aus zu erschöpfen ist, und daß Erkenntnis und Nutzen in ihr untrennbar verwoben sind.“He showed us through his scientific life that chemistry cannot be exploited fully with the aid of a single theory or a single methodology, and that it is a field in which knowledge and application are inextricably linked.” G. Bugge: Das Buch der großen Chemiker, Vol. 2, 4th reprint, Verlag Chemie, Weinheim 1974.R. Koch, writing about Louis Pasteur
    Additional Material: 14 Ill.
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  • 2
    ISSN: 0570-0833
    Keywords: Umpolung ; Nitrosamines ; Amines ; Synthetic methods ; Nucleophilic reactions ; Aminoalkylation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: There are basically two kinds of hetero atoms in organic molecules: one kind confers electrophilic character upon the carbon atom to which it is bound, and the other kind turns it into a nucleophilic site. The development of methods permitting transitions between the two resulting categories of reagents has become an important task of modern organic synthesis. The scope of such umpolung of the reactivity of functional groups is discussed for the case of amines as an example. A method of preparing masked α-secondary amino carbanions consists in nitrosation of the secondary amine, followed by metalation of the resulting nitrosamine α-to the nitrogen, reaction with electrophiles, and subsequent denitrosation. Many examples are given for each of these steps which illustrate the wide scope of the overall synthetic operation (electrophilic substitution at the α-C atom of the secondary amine). Preliminary applications and a method for avoiding the handling of nitrosamines are presented, and the report concludes with a brief account of the significance of nitrosamines in the study of carcinogenesis and mutagenesis.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0570-0833
    Keywords: Nucleophilic reactions ; Synthetic methods ; Selectivity ; Organotitanium compounds ; Organozirconium compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of carbanionic organometallic compounds (usually RLi or RMgX) to a carbonyl group - a key step in numerous syntheses - is not always straightforward. Depending on the substrate, various complications and problems may arise, but in many cases these can be remedied by addition of (RO)3TiCl, (RO)3ZrCl or (R2N)3TiX to the classic lithium and Grignard reagents. This usually leads to formation of stable organo-titanium and -zirconium compounds which react highly selectively with carbonyl groups. For example, CH3Ti(OiPr)3 reacts five orders of magnitude faster with benzaldehyde than with acetophenone at room temperature; reagents of the type RTi(OiPr)3 add smoothly to nitro-, ido-, or cyano-subsituted benzaldehyde, and the reactions may be performed in chlorinated solvents or acetonitrile; the zirconium analogues have particularly low basicity and add in high yield to α- and β-tetralones or to substrates containing a nitroaldol group; the inclusion of chiral OR* groups gives enantioselective reagents (up to 90% ee); allylic (RO3)Ti- derivatives react only at the more highly substituted carbon atom and, in addition, react diastereoselectively (up to 98% ds) with unsymmetrical ketones. Finally, titanium reagents have also been found to effect novel transformations such as direct geminal dialkylation (C=O→CMe2) and alkylative amination [C=O→CR(NR2′)]. The modification and finetuning (“taming”) of carbonyl reactivity obtainable by use of the new reagents is not dearly bought; starting materials are the cheap and harmless “titanates”, “zirconates” and the corresponding tetrachlorides.
    Additional Material: 4 Ill.
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