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

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

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

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

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 DFT calculations. An anti-cancer agent was prepared from 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