Unprecedented nucleophile-promoted 1,7-S or Se shift reactions under Pummerer reaction conditions of 4-alkenyl-3-sulfinylmethylpyrroles

Takashi Go; Akane Morimatsu; Hiroaki Wasada; Genzoh Tanabe; Osamu Muraoka; Yoshiharu Sawada; Mitsuhiro Yoshimatsu

doi:10.3762/bjoc.14.250

Unprecedented nucleophile-promoted 1,7-S or Se shift reactions under Pummerer reaction conditions of 4-alkenyl-3-sulfinylmethylpyrroles

Beilstein J Org Chem. 2018 Oct 29:14:2722-2729. doi: 10.3762/bjoc.14.250. eCollection 2018.

Authors

Takashi Go¹, Akane Morimatsu¹, Hiroaki Wasada², Genzoh Tanabe³, Osamu Muraoka³, Yoshiharu Sawada⁴, Mitsuhiro Yoshimatsu¹

Affiliations

¹ Department of Chemistry, Faculty of Education, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan.
² Department of Chemistry, Faculty of Regional Study, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan.
³ School of Pharmacy, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka 577-8502, Japan.
⁴ Life Science Research Center, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan.

Abstract

A unique 1,7-S- and Se-shift reaction under Pummerer reaction conditions of 4-alkenyl-3-sulfinyl- and seleninylpyrroles was described. The usual Pummerer reaction of 4-(alkenylaminomethyl)-3-phenylsulfinylpyrroles and a successive reaction with tetrabutylammonium hydroxide (TBAH) yielded either pyrrolo[3,2-c]azepines or N-pyrrol-3-ylmethyl-N-(4-hydroxy-3-sulfanylpropyl)-p-toluenesulfonamides (diols). Seleno-Pummerer reactions of 3-selanylmethylpyrroles also proceeded via in situ generation of selenoxides, followed by a treatment with TBAH.

Keywords: 1,7-sulfur shift; Pummerer reaction; hydroamination; pyrrole; pyrroloazepine.