Tweaking Copper Hydride (CuH) for Synthetic Gain. A Practical, One-Pot Conversion of Dialkyl Ketones to Reduced Trialkylsilyl Ether Derivatives

Abstract

[reaction: see text] Variations in the reagents and stoichiometries used to generate CuH in situ, as well as the nature of the ligands present, have led to a very efficient and inexpensive method for effecting hydrosilylations of dialkyl ketones.

Controlled Microwave Heating in Modern Organic Synthesis

“…[137] Here it was essential to use openvessel technology, since the two equivalents of the volatile byproduct ethanol that formed under normal (atmospheric pressure) conditions were simply distilled off and therefore Scheme 19. Petasis olefination, [60] hydrosilylation of ketones, [134] and Dötz benzannulation. [135] CAN = cerium ammonium nitrate, TBS = tertbutyldimethylsilyl, TES = triethylsilyl, TIPS = triisopropylsilyl.…”

Mechanism of ketone hydrosilylation by Cu(I) catalysts: A theoretical study

“…The cost of Rh catalysts, however, formed a major stumbling-block for their large scale industrialization. Over the last two decades alternative efficient asymmetric hydrosilylation reactions using titanium [4][5][6][7], zinc [8,9], tin [10], titanocene [5,11], manganese [12], and copper [11,[13][14][15][16][17] were developed.…”

“…This so called ''Stryker's reagent" calls for CuCl plus an equivalent of NaOt-Bu to generate CuOt-Bu. To avoid this extremely air-sensitive system advances have been made to form the Cu-H species in situ [21,16,17,22]. By using silanes, as a stoichiometric hydride, only catalytic quantities of the copper species are required (for a review of CuH-catalyzed reactions see Refs.…”

Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

“…The asymmetric synthesis of these compounds has been realized through a variety of methods (1, 4, 5), most notably asymmetric Mannich reactions (6-8), diastereoselective or enantioselective conjugate additions (9-13), and the reduction of ␤-amido ␣,␤-unsaturated esters or nitriles (6,(14)(15)(16)(17)(18). Although the reduction of ␣,␤-unsaturated esters has proven to be a particularly powerful tool for this transformation, the various methods used are generally limited to substrates that contain a primary amido group in the ␤ position.We recently described a versatile system for the asymmetric conjugate reduction of a wide variety of ␣,␤-unsaturated carbonyl compounds (19)(20)(21)(22)(23)(24)(25)(26)(27). Appropriately substituted acyclic ␣,␤-unsaturated esters, cyclopentenones, lactones, and lactams could all be reduced in high yield and with excellent levels of enantioselectivity.…”

“…We recently described a versatile system for the asymmetric conjugate reduction of a wide variety of ␣,␤-unsaturated carbonyl compounds (19)(20)(21)(22)(23)(24)(25)(26)(27). Appropriately substituted acyclic ␣,␤-unsaturated esters, cyclopentenones, lactones, and lactams could all be reduced in high yield and with excellent levels of enantioselectivity.…”