Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope, Limitations and Iterative Reactions. Issue 15 (1st August 2016)

• Record Type: Journal Article
• Authors: Drissi‐Amraoui, Sammy; Schmid, Thibault E.; Lauberteaux, Jimmy; Crévisy, Christophe; Baslé, Olivier; de Figueiredo, Renata Marcia; Halbert, Stéphanie; Gérard, Hélène; Mauduit, Marc; Campagne, Jean‐Marc
• Is Part Of: Advanced synthesis & catalysis. Volume 358:Issue 15(2016)
• Page Start: 2519
• Page End: 2540
• Publication Date: 2016-08-01
• Subjects: acyl-N-methylimidazole -- asymmetric conjugate addition -- copper -- 1, 3-deoxypropionates -- iterative process; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201600458
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: An efficient copper‐catalyzed enantioselective conjugate addition of dimethylzinc to unsaturated 2‐acyl‐ N ‐methylimidazoles has been achieved using a chiral bidentate hydroxyalkyl‐NHC ligand. The reactions proceed with excellent regioselectivity (1, 4 vs . 1, 6 and 1, 8) in extended conjugated systems to afford the 1, 4‐adducts in high enantioselectivities. This regioselectivity could be ascertained by DFT studies highlighting the crucial role of the imidazole ring. Thanks to the development of efficient protocols to regenerate the unsaturated 2‐acyl‐ N ‐methylimidazole moiety, an iterative process has been developed ultimately leading to 3, 5, 7 all‐syn or anti‐anti polydeoxypropionate stereodiads. Abstract :