College of Science, University of Shanghai for Science and Technology, Shanghai, 200093, P. R. China.
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore, Singapore.
Angew Chem Int Ed Engl. 2020 Aug 17;59(34):14404-14408. doi: 10.1002/anie.202006322. Epub 2020 Jul 1.
We present herein an unprecedented allylative dicarbofunctionalization of alkynes with allylic alcohols. This simple catalytic procedure utilizes commercially available Ni(COD) , triphenylphosphine, and inexpensive reagents, and delivers valuable skipped dienes and trienes with an all-carbon tetrasubstituted alkene unit in a highly stereoselective fashion. Preliminary mechanistic studies support the reaction pathway of allylnickelation followed by transmetalation in this dicarbofunctionalization of alkynes.
我们在此提出了炔烃与烯丙醇的首例前所未有的烯丙基双官能团化反应。这种简单的催化方法使用了商业可得的 Ni(COD)、三苯基膦和廉价的试剂,并以高度立体选择性的方式提供了具有全碳四取代烯烃单元的有价值的 skipped dienes 和 trienes。初步的机理研究支持了在该炔烃双官能团化反应中,烯丙基镍化后再进行转金属化的反应途径。