Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Warshel Institute for Computational Biology, Shenzhen Key Laboratory of Steroid Drug Discovery and Development, School of Life and Health Sciences, The Chinese University of Hong Kong (Shenzhen), Shenzhen 518172, China.
Org Lett. 2021 May 21;23(10):4045-4050. doi: 10.1021/acs.orglett.1c01262. Epub 2021 May 12.
A regiodivergent nickel-catalyzed hydrocyanation of 1-aryl-4-silyl-1,3-diynes is reported. When appropriate bisphosphine and phosphine-phosphite ligands are applied, the same starting materials can be converted into two different enynyl nitriles with good yields and high regioselectivities. The DFT calculations unveiled that the structural features of different ligands bring divergent alkyne insertion modes, which in turn lead to different regioselectivities. Moreover, the synthetic value of the cyano-containing 1,3-enynes has been demonstrated with several downstream transformations.
报道了一种区域发散的镍催化 1-芳基-4-硅基-1,3-二炔的加氢氰化反应。当应用适当的双膦和膦-亚磷酸配体时，相同的起始原料可以转化为两种不同的烯炔腈，产率高，区域选择性好。DFT 计算揭示了不同配体的结构特征带来了不同的炔烃插入模式，进而导致了不同的区域选择性。此外，含氰基的 1,3-烯炔的合成价值已经通过几种下游转化得到了证明。
