☆ 4.8 Article

5-(Cyano)dibenzothiophenium Triflate: A Sulfur-Based Reagent for Electrophilic Cyanation and Cyanocyclizations

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

期刊

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

卷 58, 期 28, 页码 9496-9500

出版社

WILEY-V C H VERLAG GMBH

DOI: 10.1002/anie.201904557

关键词

electrophilic cyanation; metal-free functionalizations; sulfonium salts; transfer reagents; umpolung

类别

Chemistry, Multidisciplinary

资金

European Research Council [ERC CoG 771295]
Deutsche Forschungsgerneinschaft [INST 186/1237-1]
University of Gottingen

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Protocol

Reagent

摘要

The synthesis of 5-(cyano)dibenzothiophenium triflate 9, prepared by activation of dibenzo[b,d]thiophene-5-oxide with Tf2O and subsequent reaction with TMSCN is reported, and its reactivity as electrophilic cyanation reagent evaluated. The scalable preparation, easy handling and broad substrate scope of the electrophilic cyanation promoted by 9, which includes amines, thiols, silyl enol ethers, alkenes, electron rich (hetero)arenes and polyaromatic hydrocarbons, illustrate the synthetic potential of this reagent. Importantly, Lewis acid activation of the reagent is not required for the transfer process. We additionally report herein biomimetic cyanocyclization cascade reactions, which are not promoted by typical electrophilic cyanation reagents, demonstrating the superior ability of 9 to trigger challenging transformations.

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