Synlett 2014; 25(08): 1150-1154
DOI: 10.1055/s-0033-1341065
letter
© Georg Thieme Verlag Stuttgart · New York

Allylic Substitution of Esters Derived from 2-Bromocyclohex-2-enol with Aryl Copper Reagents and Synthetic Utilization of the Derived anti SN2′ Products

Atsushi Ikoma
Department of Bioengineering, Tokyo Institute of Technology, Box B52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan   Fax: +81(45)9245789   Email: ykobayas@bio.titech.ac.jp
,
Yuichi Kobayashi*
Department of Bioengineering, Tokyo Institute of Technology, Box B52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan   Fax: +81(45)9245789   Email: ykobayas@bio.titech.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 23 January 2014

Accepted after revision: 03 March 2014

Publication Date:
03 April 2014 (online)


Abstract

Allylic substitution of esters derived from 2-bromocyclohex-2-enol with PhMgBr-based copper reagent was investigated to find high anti SN2′ selectivity with the diethyl phosphate, whereas other esters such as picolinate, acetate, and mesylate resulted in partial racemization or recovery of the starting esters. This protocol was applied to the copper reagent derived from 2-Me-4-MeOC6H3MgBr and CuBr·SMe2 and the olefin part of the anti SN2′ product was cleaved for a synthesis of patchouli alcohol.

Supporting Information