Triply Hydrogen-Bond-Directed Enantioselective Assembly of Pyrrolobenzo-1,4-diazine Skeletons with Quaternary Stereocenters

Xiaoming Shen; Yongtao Wang; Tiandi Wu; Zhenjun Mao; Xufeng Lin

doi:10.1002/chem.201500823

Triply Hydrogen-Bond-Directed Enantioselective Assembly of Pyrrolobenzo-1,4-diazine Skeletons with Quaternary Stereocenters

Chemistry. 2015 Jun 15;21(25):9039-43. doi: 10.1002/chem.201500823. Epub 2015 May 12.

Authors

Xiaoming Shen¹, Yongtao Wang¹, Tiandi Wu¹, Zhenjun Mao¹, Xufeng Lin²

Affiliations

¹ Laboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027 (P.R. China), Fax: (+86) 571-87952759.
² Laboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027 (P.R. China), Fax: (+86) 571-87952759. lxfok@zju.edu.cn.

PMID: 25965054
DOI: 10.1002/chem.201500823

Abstract

Highly efficient synthesis of optically enriched pyrrolobenzo-1,4-diazines bearing quaternary stereocenters has been realized through the chiral Brønsted acid-catalyzed Pictet-Spengler reaction of 2-(1H-pyrrol-1-yl)anilines and α-ketoamides in good to excellent yields and enantioselectivities. Computational studies suggest an unprecedented phenomenon whereby the chiral phosphoric acid catalyst employs attractive arene C-H⋅⋅⋅N hydrogen bonding to activate the substrate and induce chirality through a triple hydrogen-bonding interaction.

Keywords: Brønsted acids; Pictet-Spengler reaction; chirality; organocatalysis; phosphoric acids.

Publication types

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