Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents

Shermin S Goh; Sureshbabu Guduguntla; Takashi Kikuchi; Martin Lutz; Edwin Otten; Makoto Fujita; Ben L Feringa

doi:10.1021/jacs.8b02992

Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents

J Am Chem Soc. 2018 Jun 13;140(23):7052-7055. doi: 10.1021/jacs.8b02992. Epub 2018 May 31.

Authors

Shermin S Goh^{1

2}, Sureshbabu Guduguntla¹, Takashi Kikuchi^{3

4}, Martin Lutz⁵, Edwin Otten¹, Makoto Fujita³, Ben L Feringa¹

Affiliations

¹ Stratingh Institute for Chemistry , University of Groningen , Nijenborgh 4 , 9747 AG Groningen , The Netherlands.
² Institute of Materials Research and Engineering , 2 Fusionopolis Way, Innovis #08-03 , Singapore 138634.
³ Department of Applied Chemistry , University of Tokyo , 7-3-1, Hongo , Bukyo-ku, Tokyo 113-8656 , Japan.
⁴ Rigaku Corporation , 3-9-12 Matsubara-cho , Akishima-shi, Tokyo 196-8666 , Japan.
⁵ Bijvoet Center for Biomolecular Research , Utrecht University , Padualaan 8 , 3584 CH Utrecht , The Netherlands.

Abstract

The highly regio- and enantioselective (up to >99:1 dr, up to 99:1 er) desymmetrization of meso-1,4-dibromocycloalk-2-enes using asymmetric allylic substitution with organolithium reagents to afford enantioenriched bromocycloalkenes (ring size of 5 to 7) has been achieved. The cycloheptene products undergo an unusual ring contraction. The synthetic versatility of this Cu(I)-catalyzed reaction is demonstrated by the concise stereocontrolled preparation of cyclic amino alcohols, which are privileged chiral structures in natural products and pharmaceuticals and widely used in synthesis and catalysis.

Publication types

Research Support, Non-U.S. Gov't