An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)3 -Catalyzed [3+2] Cycloaddition of Donor-Acceptor Cyclopropanes with Thionoesters

Yohei Matsumoto; Daiki Nakatake; Ryo Yazaki; Takashi Ohshima

doi:10.1002/chem.201800957

An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)₃ -Catalyzed [3+2] Cycloaddition of Donor-Acceptor Cyclopropanes with Thionoesters

Chemistry. 2018 Apr 20;24(23):6062-6066. doi: 10.1002/chem.201800957. Epub 2018 Mar 25.

Authors

Yohei Matsumoto¹, Daiki Nakatake¹, Ryo Yazaki¹, Takashi Ohshima¹

Affiliation

¹ Graduate School of Pharmaceutical Sciences, Kyushu University Maidashi Higashi-ku, Fukuoka, 812-8582, Japan.

PMID: 29488258
DOI: 10.1002/chem.201800957

Abstract

A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf)₃ -promoted [3+2] cycloaddition of donor-acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.

Keywords: cycloaddition; iron; stereoselectivity; tetrahydrothiophenes; thionoesters.