Department of Material Chemistry, Graduate School of Engineering, Kyoto University , Kyoto 615-8510, Japan.
J Am Chem Soc. 2014 Mar 12;136(10):3732-5. doi: 10.1021/ja4122632. Epub 2014 Mar 3.
A cooperative palladium/triorganoboron catalyst to accomplish the intramolecular aminocyanation of alkenes through the cleavage of N-CN bonds is reported. 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) is found to be crucial as a ligand for palladium to effectively catalyze the transformation with high chemo- and regioselectivity. A range of substituted indolines and pyrrolidines with both tetra- or trisubstituted carbon and cyano functionalities are readily furnished by the newly developed cyanofunctionalization reaction. A preliminary example of enantioselective aminocyanation is also described.
报道了一种通过 N-CN 键断裂实现烯烃分子内氨基氰化的钯/三有机硼协同催化剂。发现 4,5-双（二苯基膦基）-9,9-二甲基氧杂蒽（Xantphos）作为配体对于钯的有效催化至关重要，可高化学选择性和区域选择性地催化该转化。通过新开发的氰基官能化反应，可以很容易地得到具有四取代或三取代碳和氰基官能团的取代吲哚啉和吡咯烷。还描述了一个对映选择性氨基氰化的初步实例。
