Stereospecific Overman Rearrangement of Substituted Cyclic Vinyl Bromides: Access to Fully Substituted α-Amino Ketones

• DOI: 10.1021/acs.orglett.9b03347
• Publication Date: 2019-10-30T12:50:50Z
• Authors: Álvaro Velasco-Rubio; Eric J. Alexy; Makoto Yoritate; Austin C. Wright; Brian M. Stoltz
• Keywords: 540; 01 natural sciences; 0104 chemical sciences

A versatile thermal Overman rearrangement of enantioenriched, cyclic allylic alcohols providing tertiary allylic amines has been developed. The vinyl bromide used to control enantioselectivity in a preceding CBS reduction is utilized as a synthetic handle for the preparation of tertiary α-amino ketones and related derivatives in an asymmetric fashion.