In recent years our group reported highly enantioselective methods for the synthesis of enantioenriched tertiary alcohols, α-tertiary amines and heteroaryl alkanes via copper(I)-catalyzed addition of a Grignard reagent to an electrophile. Compounds bearing an electron rich atom, like oxygen or nitrogen, can interact with a copper(I)/phosphine complex to form a new catalyst. Asymmetric auto-inductive effects are reported for a number of organometallic reactions where the functionalities of the products resemble the ones of the catalyst, for instance addition of organozinc reagents to ketones catalyzed by an amino alcohol. Herein we will report auto-inductive effects in the catalytic asymmetricalkylation of ketones and aldehydes with Grignard reagents. Mechanistic studies which pointed at formation of a new chiral catalyst formed through an interaction between the reaction product (an alkoxide) and an initial chiral catalyst (copper/phosphine complex) will be discussed as well.

Asymmetric autoinduction in the copper/phosphine catalyzed alkylation of carbonyl compounds

254th National Meeting (2017)

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