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Complex Reducing Agents (CRA's)—Versatile, Novel Ways of Using Sodium Hydride in Organic Synthesis
Author(s) -
Caubère Paul
Publication year - 1983
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198305991
Subject(s) - reagent , chemistry , hydride , sodium hydride , carbonylation , halide , organic synthesis , regioselectivity , combinatorial chemistry , sodium , aryl , catalysis , organic chemistry , medicinal chemistry , metal , carbon monoxide , alkyl
Why do we hardly use the simplest and, at the same time, inexpensive reducing agent sodium hydride in organic chemistry? To this question the answer is invariably: “It is too basic”. In this progress report we describe work we have performed aimed at controlling the basicity of NaH using sodium alcoholates and metal salts. The complex r educing a gents (CRA's) developed (symbolized NaH‐RONa‐MX n ) allow organic halides, alkenes, alkynes and ketones to be reduced selectively. Highly regioselective 1,4‐ and 1,2‐reductions of α,β‐unsaturated ketones are easily performed using appropriate metal salts. Modified CRA's have proved to be excellent hydrosilylating reagents for carbonyl groups, non‐pyrophoric heterogeneous hydrogenation catalysts, coupling reagents for aryl and vinyl halides, and reagents for the carbonylation of organic halides under very mild conditions. The study of these reactions opened up the field to phase‐transfer‐catalyzed photostimulated carbonylations as well as to S RN 1 reactions of metalates.–Thus, starting from the simple sodium hydride a large number of useful reagents have become accessible.