Copper-catalyzed asymmetric conjugate addition of Grignard reagents to cyclic enones
- 9 April 2004
- journal article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences
- Vol. 101 (16) , 5834-5838
- https://doi.org/10.1073/pnas.0308008101
Abstract
It is no longer necessary to use dialkylzinc reagents to obtain enantioselectivities >95% in the copper-catalyzed asymmetric conjugate addition of organometallic compounds to cyclic enones. We now report how this can be accomplished by using inexpensive and readily available Grignard reagents. Screening of bidentate ligands provided outstanding results with copper complexes of commercially available chiral ferrocenyl-based diphosphines, in particular TaniaPhos and JosiPhos derivatives. These catalysts tolerate a range of Grignard reagents and different cyclic enones as substrates, leading to high regioselectivities and unprecedented enantioselectivities. Moreover, the reactions are successful with moderate catalyst loading (5 mol %) under mild conditions and in the absence of additives.Keywords
This publication has 52 references indexed in Scilit:
- Highly Enantioselective Conjugate Addition of Dialkylzinc Reagents to Acyclic Nitroalkenes: A Catalytic Route to β2-Amino Acids, Aldehydes, and AlcoholsJournal of the American Chemical Society, 2003
- Cu−Catalyzed Enantioselective Conjugate Addition of Alkylzincs to Cyclic Nitroalkenes: Catalytic Asymmetric Synthesis of Cyclic α-Substituted KetonesJournal of the American Chemical Society, 2002
- Ferrocenyl Ligands with Two Phosphanyl Substituents in theα,ɛ positions for the Transition Metal Catalyzed Asymmetric Hydrogenation of Functionalized Double BondsAngewandte Chemie International Edition in English, 1999
- A New Method for Synthesis of Functionalized Organozinc-Copper(I) Reagents and Their 1,4-Addition Reaction with EnonesSynthetic Communications, 1998
- Ni-Catalyzed Asymmetric Addition of Grignard Reagents to Unsaturated Cyclic Acetals. The Influence of Added Phosphine on EnantioselectivityJournal of the American Chemical Society, 1998
- Copper-Catalyzed Enantioselective Michael Additions: Recent Progress with New Phosphorus LigandsAngewandte Chemie International Edition in English, 1998
- Enantioselective 1,4‐Addition of Aliphatic Grignard Reagents to Enones Catalyzed by Readily Available Copper(I) thiolates derived from TADDOL. Preliminary communicationHelvetica Chimica Acta, 1997
- A new class of organocopper and organocuprate compounds derived from copper(I) arenethiolatesJournal of the American Chemical Society, 1992
- Enantioselective conjugate addition of Grignard reagents to enones catalyzed by chiral zinc(II) complexesThe Journal of Organic Chemistry, 1990
- Enzymes in organic synthesis. 14. Stereoselective horse liver alcohol dehydrogenase catalyzed oxidations of diols containing a prochiral centre and of related hemiacetalsCanadian Journal of Chemistry, 1979