Copper mediated carbometalation reactions

Abstract

This tutorial review gives an overview on copper-mediated carbometalation reactions with a special emphasis on carbometalation of cyclopropenes.

Diastereodivergent combined carbometalation/zinc homologation/C–C fragmentation reaction as an efficient tool to prepare acyclic allylic quaternary carbon stereocenters

“…When 1a was treated at –45 °C in THF with 1.05 equivalents of MeCu, easily prepared by mixing MeLi and CuI in a 1 : 1 ratio, the carbometalated product 2a anti was rapidly obtained after hydrolysis (less than 30 minutes) with a very high anti -diastereoselectivity in good yield ( Table 1 , entry 1). 21 The configuration of 2a anti was established by NOE experiments (see ESI † ). The preferential formation of diastereomer 2a anti can only be possible if the carbometalation reaction is sterically driven.…”

Diastereo- and enantioselective copper catalyzed hydroallylation of disubstituted cyclopropenes

“… 14 – 21 An alternative approach consists in the manipulation of an existing scaffold and in this context the carbometalation of cyclopropenes has proven to be a very efficient method leading to a large variety of polysubstituted cyclopropane derivatives from a single precursor. 22 , 23 Our group 24 – 33 and others 34 – 40 have contributed to the last approach by reporting several transition-metal catalyzed protocols for the addition of carbon nucleophiles to cyclopropenes with high diastereo- and enantioselectivities ( Scheme 1a ). However, as the incoming alkyl residues (nucleophiles) and the organometallic species are always introduced in a cis -relationship across the unsaturation, all the above discussed strategies of carbometalation provide only access to 1,2- syn functionalized cyclopropanes.…”

Theoretical Calculations on the Mechanism of Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones

“…Among the series of organometallic catalysis reactions, copper catalysis has offered an inexpensive, environmentally friendly alternative to the use of precious metals [25][26][27][28][29][30][31][32][33][34]. Shibasaki et al described a possible solution to a catalytic enantioselective allylation of ketoimines.…”