Dehydrative Cross-coupling of Allylic Alcohols with Alkynes

Peizhong Xie*^a, Zuolian Sun^a, Shuangshuang Li^a, Lei Zhang^b, Xinying Cai^a, Weishan Fu^a, Xiaobo Yang^a, Yanan Liu^a, Xiangyang Wo^a_,and Teck-Peng Loh*^ac

^aSchool of Chemistry and Molecular Engineering, Institute of Advanced Synthesis, Nanjing Tech University, Nanjing 211816, P. R. China.

^bSchool of Science, Tianjin Chengjian University, Tianjin 300384, P. R. China.

^cDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371.

Abstract:Ahighly efficient Pd/Ca catalytic system for the directlydehydrativecross-couplingof allylic alcohols with terminal alkyneswas developed. This calcium saltcocatalyst facilitates the oxidative addition of the palladium catalyst (1 mol%) totheC-OH bond.Then, the insitu-generated hydroxide ion deprotonates the terminal alkynes to promote the formation oftheallylalkynylpalladium intermediate, liberating water as the only byproduct. This proposed mechanism is also supported by DFTcalculations.An anti-cancer agentwas preparedfrom inexpensive starting materials on a 10-gram scale.

Org. Lett,2020,22, 1599-1604（影响因子：6.555）

论文链接：https://pubs.acs.org/doi/10.1021/acs.orglett.0c00108