Regiodivergent Intermolecular [3+2] Cycloadditions of Vinyl Aziridines and Allenes: Stereospecific Synthesis of Chiral Pyrrolidines

Tao-Yan Lin; Chao-Ze Zhu; Peichao Zhang; Yidong Wang; Hai-Hong Wu; Jian-Jun Feng; Junliang Zhang

doi:10.1002/anie.201605530

Regiodivergent Intermolecular [3+2] Cycloadditions of Vinyl Aziridines and Allenes: Stereospecific Synthesis of Chiral Pyrrolidines

Angew Chem Int Ed Engl. 2016 Aug 26;55(36):10844-8. doi: 10.1002/anie.201605530. Epub 2016 Aug 3.

Authors

Tao-Yan Lin¹, Chao-Ze Zhu¹, Peichao Zhang¹, Yidong Wang¹, Hai-Hong Wu¹, Jian-Jun Feng², Junliang Zhang^{3

4}

Affiliations

¹ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, P.R. China.
² Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, P.R. China. jjfeng@chem.ecnu.edu.cn.
³ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, P.R. China. jlzhang@chem.ecnu.edu.cn.
⁴ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai, 200032, China. jlzhang@chem.ecnu.edu.cn.

PMID: 27485044
DOI: 10.1002/anie.201605530

Abstract

The first rhodium-catalyzed intermolecular [3+2] cycloaddition reaction of vinyl aziridines and allenes for the synthesis of enantioenriched functionalized pyrrolidines was realized. [3+2] cycloaddition with the proximal C=C bond of N-allenamides gave 3-methylene-pyrrolidines in high regio- and diastereoselectivity, whereas, 2-methylene-pyrrolidines were obtained as the major products by the cycloadditions of vinyl aziridines with the distal C=C bond of allenes. Use of readily available starting materials, a broad substrate scope, high selectivity, mild reaction conditions, as well as versatile functionalization of the cycloadducts make this approach very practical and attractive.

Keywords: allenes; chirality; cycloaddition; heterocycles; rhodium.

Publication types

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