Design of Modified Amine Transfer Reagents Allows the Synthesis of alpha-Chiral Secondary Amines via CuH-Catalyzed Hydroamination

作者：Niu Dawen; Buchwald Stephen L^*

来源：Journal of the American Chemical Society, 2015, 137(30): 9716-9721.

DOI：10.1021/jacs.5b05446

The CuH-catalyzed hydroamination of alkenes and alkynes using a silane and an amine transfer reagent represents a, simple Strategy to access chiral amine products. We have recently reported methods to prepare chiral amines with-thigh efficiency and stereoselectivity using this approach. However, the:current technology is limited to the synthesis of trialkylamines from dialkylamine transfer reagents (R(2)NOBz). When monoalkylamine transfer reagents, [RN(H)OBz] were used for the synthesis of chiral secondary amines, competitive; nonproductive,consumption of these reagents by the CuH species resulted in poor yields. In this paper, we report the design of a Modified type of amine transfer reagent that addresses this limitation. This effort has enabledus to develop a CuH-catalyzed synthesis of chiral Secondary amines using a variety of amine coupling partners; including those derived from amino acid esters, carbohydrates, and steroids. Mechanistic investigations indicated that the modified amine transfer reagents are less susceptible to direct reaction with CuH.

• 出版日期2015-8-5