A redox-mediated molecular brake: Dynamic NMR study of 2-[2-(methylthio)phenyl]isoindolin-1-one and S-oxidized counterparts

Document Type

Article

Publication Date

10-17-2003

Abstract

A redox-mediated molecular brake based on the sulfide-sulfoxide redox cycle is illustrated by modulation of the rotation rate of an N-Ar "shaft" by varying the oxidation state of sulfur in 2-[2-(sulfur-substituted)phenyl]-isoindolin-1-ones. N-Ar rotational barriers in methylsulfinyl (2) and methylsulfonyl (3) derivatives (13.6 kcal mol -1) are ∼5 kcal mol-1 higher than sulfide 1. Rate reduction for N-Ar rotation is ∼104 s-1 (280 K) upon oxidation. Correlated N-pyramidalization/N-Ar rotation reduces the effectiveness of the brake by decreasing the energy barrier to N-Ar bond rotation.

Publication Title

Journal of Organic Chemistry

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