Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences , Nanyang Technological University , 21 Nanyang Link , Singapore 637371 , Singapore.
Org Lett. 2018 Oct 5;20(19):6188-6192. doi: 10.1021/acs.orglett.8b02668. Epub 2018 Sep 20.
The addition of arylzinc reagents ArZnCl 1 to alkynes 2 was found to be catalyzed by rhodium complexes in the presence of a catalytic amount of zinc chloride. The selectivity in giving 2-arylalkenylzinc species 3 or ortho-alkenylarylzinc species 4, the latter of which is generated through 1,4-Rh migration from alkenyl to aryl in the catalytic cycle, is controlled by the ligands on rhodium. Ligands cod and binap gave 3 and 4, respectively, with high selectivity.
芳基锌试剂 ArZnCl1 与炔烃 2 的加成反应在铑配合物的催化下,在催化量的氯化锌存在下被发现。通过催化循环中烯基到芳基的 1,4-Rh 迁移生成的邻烯基芳基锌物种 4 的选择性,控制着铑上配体的选择。cod 和 binap 配体分别给出了 3 和 4,具有很高的选择性。