Asymmetric Hydrogenation of Vinylthioethers: Access to Optically Active 1,5-Benzothiazepine Derivatives

Wei Li; Christoph Schlepphorst; Constantin Daniliuc; Frank Glorius

doi:10.1002/anie.201512032

Asymmetric Hydrogenation of Vinylthioethers: Access to Optically Active 1,5-Benzothiazepine Derivatives

Angew Chem Int Ed Engl. 2016 Mar 1;55(10):3300-3. doi: 10.1002/anie.201512032. Epub 2016 Feb 5.

Authors

Wei Li¹, Christoph Schlepphorst¹, Constantin Daniliuc¹, Frank Glorius²

Affiliations

¹ Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149, Münster, Germany.
² Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149, Münster, Germany. glorius@uni-muenster.de.

PMID: 26846168
DOI: 10.1002/anie.201512032

Abstract

A novel asymmetric hydrogenation of vinylthioethers was developed using a ruthenium(II) NHC complex. This method provides an efficient approach to optically active 1,5-benzothiazepines featuring stereocenters with C-S bonds. Excellent enantioselectivities (up to 95 % ee) and high yields (up to 99 %) were obtained for a variety of substrates bearing a range of useful functional groups. Moreover, this methodology could be directly applied to the synthesis of the antidepressant drug R-(-)-thiazesim.

Keywords: 1,5-benzothiazepine; N-heterocyclic carbenes; asymmetric hydrogenation; ruthenium; vinylthioethers.

Publication types

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

MeSH terms

Ethers / chemistry*
Hydrogenation
Stereoisomerism
Thiazepines / chemistry*

Substances

1,5-benzothiazepine
Ethers
Thiazepines