Bercot Eric A, Rovis Tomislav
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
J Am Chem Soc. 2005 Jan 12;127(1):247-54. doi: 10.1021/ja044588b.
A nickel-catalyzed alkylation of succinic and glutaric anhydrides with alkyl- and arylzinc reagents has been developed. A dramatic olefin effect has been investigated resulting in the identification of several styrene-based promoters which show pronounced enhancements in reaction rate. The substrate scope with respect to electrophilic and nucleophilic coupling partners has been examined and found to be remarkably broad, allowing for rapid introduction of molecular complexity through the use of functionalized coupling partners. Regioselective alkylation of an unsymmetrical succinic anhydride and a profound effect of pendent coordinating olefins on reaction rate suggest a mechanism involving discrete oxidative addition of the nickel complex into the cyclic anhydride followed by a transmetalation event.
已开发出一种镍催化的琥珀酸酐和戊二酸酐与烷基锌和芳基锌试剂的烷基化反应。研究了显著的烯烃效应,从而鉴定出几种基于苯乙烯的促进剂,这些促进剂在反应速率上有显著提高。已考察了亲电和亲核偶联伙伴的底物范围,发现其非常广泛,通过使用功能化偶联伙伴能够快速引入分子复杂性。不对称琥珀酸酐的区域选择性烷基化以及侧链配位烯烃对反应速率的深远影响表明,其机理涉及镍配合物向环状酸酐的离散氧化加成,随后是金属转移过程。