Nickel-catalysed migratory hydroalkynylation and enantioselective hydroalkynylation of olefins with bromoalkynes.
Nickel-catalysed migratory hydroalkynylation and enantioselective hydroalkynylation of olefins with bromoalkynes.
复制标题
镍催化的迁移加氢炔化和烯烃与溴代炔的对映选择性加氢炔化
DOI：
10.1038/s41467-021-24094-9
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发表时间：
2021-06-18
影响因子：
16.6
通讯作者：
Zhu S
中科院分区：
文献类型：
--
作者：
Jiang X;Han B;Xue Y;Duan M;Gui Z;Wang Y;Zhu S
α-手性炔是许多生物活性化合物、化学探针和功能材料的关键结构单元，也是有机合成中有价值的合成子。在这里，我们报告了一个NiH催化的还原迁移氢炔基化的烯烃与溴炔，提供了相应的苄基炔基化产物在高产率与优异的区域选择性。苯乙烯的催化对映选择性氢化炔基化反应也已经使用简单的手性PyrOx配体实现。所得到的对映体富集的苄基炔是多用途的合成中间体，并且可以容易地转化为合成有用的手性取代基。带有α立体中心的手性炔基通常存在于许多生物活性化合物、化学探针和功能材料中。在这里，作者展示了NiH催化的烯烃与溴代炔的还原迁移氢炔基化，其以高产率和优异的区域选择性形成苄基炔基化产物。
α-Chiral alkyne is a key structural element of many bioactive compounds, chemical probes, and functional materials, and is a valuable synthon in organic synthesis. Here we report a NiH-catalysed reductive migratory hydroalkynylation of olefins with bromoalkynes that delivers the corresponding benzylic alkynylation products in high yields with excellent regioselectivities. Catalytic enantioselective hydroalkynylation of styrenes has also been realized using a simple chiral PyrOx ligand. The obtained enantioenriched benzylic alkynes are versatile synthetic intermediates and can be readily transformed into synthetically useful chiral synthons. Chiral alkyne motifs bearing an α stereocentre are often found in many bioactive compounds, chemical probes, and functional materials. Here the authors show NiH-catalysed reductive migratory hydroalkynylation of olefins with bromoalkynes that form benzylic alkynylation products in high yield and with excellent regioselectivity.