McCammant Matthew S, Sigman Matthew S
Department Of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, USA. ; Tel: +1 801-585-0774.
Chem Sci. 2015 Feb;6(2):1355-1361. doi: 10.1039/C4SC03074E.
Palladium-catalyzed 1,4-difunctionalizations of isoprene that produce skipped polyenes are reported. Complex isomeric product mixtures are possible as a result of the difficult-to-control migratory insertion of isoprene into a Pd-alkenyl bond, but good site selectivity has been achieved using easily accessible Pyrox ligands. Mechanistic studies suggest that the control of insertion is the result of the unique electronic asymmetry and steric properties of the ligand.
报道了钯催化异戊二烯的1,4-双官能化反应，该反应生成了多烯。由于异戊二烯向钯-烯基键的迁移插入难以控制，可能会产生复杂的异构体产物混合物，但使用易于获得的Pyrox配体已实现了良好的位点选择性。机理研究表明，插入的控制是配体独特的电子不对称性和空间性质的结果。
