Department of Chemistry & Biochemistry, Duquesne University , Pittsburgh, Pennsylvania 15282-1530, United States.
Org Lett. 2014 Jan 3;16(1):62-5. doi: 10.1021/ol403020s. Epub 2013 Dec 12.
The addition of BuLi, Bu3MgLi, Et2ZnBuLi, or Me2CuLi to α-arylthioalkanenitriles triggers an arylthio-metal exchange. NMR spectroscopic analyses implicate organometallic attack on sulfur forming a three-coordinate sulfidate as the key intermediate. Electrophilic trapping affords tertiary and quaternary nitriles in high yield. The method addresses the challenge of improving the functional group tolerance and preventing polyalkylations.
BuLi、Bu3MgLi、Et2ZnBuLi 或 Me2CuLi 的添加会引发α-芳基硫代烷腈的芳基硫-金属交换。NMR 光谱分析表明，硫原子的亲核进攻形成了三配位的亚磺酸盐作为关键中间体。亲电试剂的捕获以高产率得到了叔腈和季腈。该方法解决了提高官能团容忍度和防止多烷基化的难题。
