Synthesis 2014; 46(14): 1917-1923
DOI: 10.1055/s-0033-1338638
special topic
© Georg Thieme Verlag Stuttgart · New York

An Unexpected Inversion of Enantioselectivity in a Copper-Catalyzed Intramolecular­ Desymmetric Aryl C–N Coupling Reaction

Jiangguang Liu
a  Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, No. 190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou 510530, P. R. of China   Fax: +86(20)32015266   Email: cai_qian@gibh.ac.cn
,
Jiajie Yan
a  Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, No. 190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou 510530, P. R. of China   Fax: +86(20)32015266   Email: cai_qian@gibh.ac.cn
,
Dongguang Qin
a  Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, No. 190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou 510530, P. R. of China   Fax: +86(20)32015266   Email: cai_qian@gibh.ac.cn
b  ABA Chemicals Corporation, Suite 18, Ningxia Road, Shanghai 200063, P. R. of China
,
Qian Cai
a  Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, No. 190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou 510530, P. R. of China   Fax: +86(20)32015266   Email: cai_qian@gibh.ac.cn
› Author Affiliations
Further Information

Publication History

Received: 20 February 2014

Accepted: 15 April 2014

Publication Date:
09 May 2014 (online)

Abstract

Enantioselective formation of indolines was achieved through desymmetrization of α,α-bis(2-iodobenzyl)glycines under the catalysis of copper(I) iodide and (2S,3aS,7aS)-octahydro-1H-­indole-2-carboxylic acid. An unexpected inversion of enantioselectivity was observed when achiral additives such as 4-(N,N-dimethylamino)pyridine were added which work together with the ligand. The configuration-reversed products were obtained in moderate yields as well as moderate ee values.

Supporting Information

 
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