Catalytic, enantioselective, intramolecular carbosulfenylation of olefins. preparative and stereochemical aspects

Scott E Denmark, Alex Jaunet

Research output: Contribution to journalArticle

Abstract

The first catalytic, enantioselective, intramolecular carbosulfenylation of isolated alkenes with aromatic nucleophiles is described. The combination of N-phenylsulfenylphthalimide, a chiral selenophosphoramide derived from BINAM, and ethanesulfonic acid as a cocatalytic Brønsted acid induced an efficient and selective cyclofunctionalization of various alkenes (aliphatic and aromatic) tethered to a 3,4-methylenedioxyphenyl ring. Under these conditions, 6-phenylthio-5,6,7,8-tetrahydronaphthalenes are formed diastereospecifically in good yields (50-92%) and high enantioselectivities (71:29-97:3 er). E-Alkenes reacted much more rapidly and with much higher selectivity than Z-alkenes, whereas electron-rich alkenes reacted more rapidly but with comparable selectivity to electron-neutral alkenes and electron-deficient alkenes. The Brønsted acid played a critical role in effecting reproducible enantioselectivity. A model for the origin of enantioselectivity and the dependence of rate and selectivity on alkene structure is proposed along with a rationale for the site selectivity in reactions with monoactivated arene nucleophiles.

Original languageEnglish (US)
Pages (from-to)140-171
Number of pages32
JournalJournal of Organic Chemistry
Volume79
Issue number1
DOIs
StatePublished - Jan 3 2014

    Fingerprint

ASJC Scopus subject areas

  • Organic Chemistry

Cite this