Dehydrative Cross-Coupling of Allylic Alcohols with Alkynes
Peizhong Xie, Zuolian Sun, Shuangshuang Li, Lei Zhang, Xinying Cai, Weishan Fu, Xiaobo Yang, Yanan Liu, Xiangyang Wo, Teck‐Peng Loh
Abstract
A highly efficient Pd/Ca catalytic system for the directly dehydrative cross-coupling of allylic alcohols with terminal alkynes was developed. This calcium salt cocatalyst facilitates the oxidative addition of the palladium catalyst (1 mol %) to the C-OH bond. Then, the in situ-generated hydroxide ion deprotonates the terminal alkynes to promote the formation of the allylalkynylpalladium intermediate, liberating water as the only byproduct. This proposed mechanism is also supported by density functional theory calculations. An anticancer agent was prepared from inexpensive starting materials on a 10 g scale.
Topics & Concepts
Allylic rearrangementChemistryCatalysisSalt (chemistry)HydroxideCoupling (piping)PalladiumCombinatorial chemistryMedicinal chemistryPolymer chemistryOrganic chemistryMechanical engineeringEngineeringCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsCatalytic Alkyne Reactions