Chirality recognition of winding vine-shaped heterobiaryls with molecular asymmetry. Kinetic and dynamic kinetic resolution by Shi's asymmetric epoxidation

Kazuki Maruhashi; Yoichi Okayama; Ryo Inoue; Shiomi Ashida; Yuka Toyomori; Kentaro Okano; Atsunori Mori

doi:10.1038/s41598-018-19878-x

Chirality recognition of winding vine-shaped heterobiaryls with molecular asymmetry. Kinetic and dynamic kinetic resolution by Shi's asymmetric epoxidation

Sci Rep. 2018 Jan 26;8(1):1704. doi: 10.1038/s41598-018-19878-x.

Authors

Kazuki Maruhashi¹, Yoichi Okayama¹, Ryo Inoue¹, Shiomi Ashida¹, Yuka Toyomori¹, Kentaro Okano¹, Atsunori Mori²

Affiliations

¹ Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe, 657-8501, Japan.
² Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe, 657-8501, Japan. amori@kobe-u.ac.jp.

Abstract

The chirality of winding vine-shaped heterobiaryls with molecular asymmetry is recognized by a sugar-based chiral oxidant. Kinetic resolution of (±)-bisbenzoimidazole bearing an olefin moiety takes place with Shi's asymmetric epoxidation to observe k_rel value up to ca. 35 affording the corresponding epoxide. The reaction of a (±)-bithiophene derivative also recognized the chirality to give the corresponding epoxide with er of 96:4 at 39% conversion. Dynamic kinetic resolution is found to take place when unsymmetrical biaryl composed of benzoimidazole/thiophene is subjected to Shi's epoxidation, whose conversion of the racemic substrate exceeds to 50%.

Publication types

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