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

Jiangguang Liu; Jiajie Yan; Dongguang Qin; Qian Cai

doi:10.1055/s-0033-1338638

Synthesis, Table of Contents

Synthesis 2014; 46(14): 1917-1923
DOI: 10.1055/s-0033-1338638

special topic

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

Jiangguang Liu

^aGuangzhou 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

^aGuangzhou 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

^aGuangzhou 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

^bABA Chemicals Corporation, Suite 18, Ningxia Road, Shanghai 200063, P. R. of China

,

Qian Cai

^aGuangzhou 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

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Abstract

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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.

Key words

asymmetric desymmetrization - indolines - copper catalysis - N-arylation - inversion

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References

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Supplementary Material

Supporting Information

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

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