Catalytic, Enantioselective, Intramolecular Sulfenofunctionalization of Alkenes with Phenols

Scott E. Denmark, David J.P. Kornfilt

Research output: Contribution to journalArticle

Abstract

The catalytic, enantioselective, cyclization of phenols with electrophilic sulfenophthalimides onto isolated or conjugated alkenes affords 2,3-disubstituted benzopyrans and benzoxepins. The reaction is catalyzed by a BINAM-based phosphoramide Lewis base catalyst which assists in the highly enantioselective formation of a thiiranium ion intermediate. The influence of nucleophile electron density, alkene substitution pattern, tether length and Lewis base functional groups on the rate, enantio- and site-selectivity for the cyclization is investigated. The reaction is not affected by the presence of substituents on the phenol ring. In contrast, substitutions around the alkene strongly affect the reaction outcome. Sequential lengthening of the tether results in decreased reactivity, which necessitated increased temperatures for reaction to occur. Sterically bulky aryl groups on the sulfenyl moiety prevented erosion of enantiomeric composition at these elevated temperatures. Alcohols and carboxylic acids preferentially captured thiiranium ions in competition with phenolic hydroxyl groups. An improved method for the selective C(2) allylation of phenols is also described.

Original languageEnglish (US)
Pages (from-to)3192-3222
Number of pages31
JournalJournal of Organic Chemistry
Volume82
Issue number6
DOIs
StatePublished - Mar 17 2017

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Phenols
Alkenes
Lewis Bases
Cyclization
Benzoxepins
Substitution reactions
Allylation
Ions
Benzopyrans
Nucleophiles
Carboxylic Acids
Phenol
Hydroxyl Radical
Functional groups
Carrier concentration
Erosion
Alcohols
Temperature
Catalysts
Chemical analysis

ASJC Scopus subject areas

  • Organic Chemistry

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Catalytic, Enantioselective, Intramolecular Sulfenofunctionalization of Alkenes with Phenols. / Denmark, Scott E.; Kornfilt, David J.P.

In: Journal of Organic Chemistry, Vol. 82, No. 6, 17.03.2017, p. 3192-3222.

Research output: Contribution to journalArticle

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