Facile Generation and Isolation of π-Allyl Complexes from Aliphatic Alkenes and an Electron-Deficient Rh(III) Complex: Key Intermediates of Allylic C–H Functionalization

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• 作者：Yu Shibata ; Eiji Kudo ; Haruki Sugiyama ; Hidehiro Uekusa ; Ken Tanaka
• 刊名：Organometallics
• 出版年：2016
• 出版时间：May 23, 2016
• 年：2016
• 卷：35
• 期：10
• 页码：1547-1552
• 全文大小：453K
• 年卷期：0
• ISSN：1520-6041

文摘

It has been established that a strongly electrophilic η⁵-cyclopentadienylrhodium complex, [Cp^ERhCl₂]_2, is capable of reacting with aliphatic alkenes in the presence of a silver salt and cesium acetate at room temperature to give the corresponding π-allyl complexes in high yields. The use of an alkenyltosylamide as the alkene also afforded the corresponding π-allyl complex. Treatment of the thus obtained π-allyl complex with a silver(I) salt and copper(II) acetate afforded the allylic amination product, which proves the intermediacy of this π-allyl complex in the rhodium(III)-catalyzed intramolecular oxidative allylic amination.