palladium catalyzed allylic c-h alkylation a mechanistic perspective钯催化烯丙基的碳氢键烷基化一个机械的视角.pdf

Molecules 2011, 16, 951-969; doi:10.3390/molecule OPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Review Palladium Catalyzed Allylic C-H Alkylation: A Mechanistic Perspective Casper Junker Engelin and Peter Fristrup * Department of Chemistry, Technical University of Denmark, Kemitorvet building 201, DK-2800, Kgs. Lyngby, Denmark * Author to whom correspondence should be addressed; E-Mail: pf@kemi.dtu.dk; Tel.: +45 Fax: +45 Received: 30 November 2010; in revised from: 13 January 2011 / Accepted: 18 January 2011 / Published: 21 January 2011 Abstract: The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium- catalyzed C-H activation, the allylic C-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage