Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron-Deficient η5-Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions

• Published in: Chemistry : a European journal Vol. 21; no. 25; pp. 9053 - 9056
• Main Authors: Takahama, Yuji, Shibata, Yu, Tanaka, Ken
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 15.06.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: alkenes; anilides; Chemistry; Chemistry, Multidisciplinary; CH bond functionalization; olefination; Physical Sciences; rhodium; Science & Technology; SELECTIVE OLEFINATION; ARENES; C-H OLEFINATION; alkenes; CH bond functionalization; DIRECTING GROUPS; anilides; COUPLING REACTION; ETA-CYCLOPENTADIENYL)RHODIUM(III) CATALYST; BOND ACTIVATION; DERIVATIVES; ALKENYLATION; olefination; rhodium
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201501232

The oxidative olefination of sp2 CH bonds of anilides with both activated and unactivated alkenes using an (electron‐deficient η5‐cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron‐deficient rhodium(III) catalyst, [Cp*RhCl2]2 showed no activity against olefination with unactivated alkenes. In addition, the deuterium kinetic isotope effect (DKIE) study revealed that the CH bond cleavage step is thought to be the turnover‐limiting step. It takes two: It has been established that a dinuclear (electron‐deficient η5‐cyclopentadienyl)RhIII complex is a highly active precatalyst for the oxidative sp2 CH bond olefination of anilides with both activated and unactivated alkenes under ambient conditions (at room temperature under air; see scheme). In contrast, a commonly employed RhIII precatalyst, [{Cp*RhCl2}2], showed no activity against olefination with unactivated alkenes.