Ketone Synthesis by Direct, Orthogonal Chemoselective Hydroacylation of Alkenes with Amides: Use of Alkenes as Surrogates of Alkyl Carbanions

• Published in: Chinese journal of chemistry Vol. 37; no. 8; pp. 811 - 816
• Main Authors: Geng, Hui, Huang, Pei‐Qiang
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH & Co. KGaA 01.08.2019; Wiley; Wiley Subscription Services, Inc
• Subjects: Activated carbon; Alkenes; Ambient temperature; Amides; Camphene; Carbonyl compounds; Carbonyls; Chemistry; Chemistry, Multidisciplinary; Ketones; Physical Sciences; Reagents; Science & Technology; Synthesis; ORGANOMETALLIC REAGENTS; SECONDARY AMIDES; DIRECT TRANSFORMATION; VERSATILE; TERTIARY AMIDES; CHEMISTRY; KETIMINES; DERIVATIVES; UNACTIVATED ALKENES; GRIGNARD
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.201900252

Summary of main observation and conclusion Direct functionalization of alkenes and direct transformation of carboxamides are two exciting areas that have attracted considerable attention in recent years. We report herein that secondary amides, the least reactive derivatives of carbonyl compounds, upon activated with triflic anhydride, can serve as effective hydroacylating reagents in partner with alkenes to yield ketones at ambient temperature. The method was applied to the one‐step synthesis of racemic dihydro‐ar‐turmerone. In this method, alkenes serve as surrogates of organometallic reagents, which allows the orthogonal chemoselective reactions. The ready availability of many olefins such as camphene and norbornene permits one‐step ketone synthesis that would require several steps by conventional methods. We report the Tf2O‐mediated hydroacylation of alkenes with secondary amides, which constitutes a mild and versatile method for ketone synthesis. The use of cheap feedstock alkenes as surrogates of organometallic reagents for selective addition to secondary amides, the least reactive carboxylic acid derivatives, presents several advantages.