Lin Xiaobin, An Kun, Zhuo Qingde, Nishiura Masayoshi, Cong Xuefeng, Hou Zhaomin
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Angew Chem Int Ed Engl. 2023 Aug 21;62(34):e202308488. doi: 10.1002/anie.202308488. Epub 2023 Jul 17.
The asymmetric hydrophosphination of cyclopropenes with phosphines is of much interest and importance, but has remained hardly explored to date probably because of the lack of suitable catalysts. We report here the diastereo- and enantioselective hydrophosphination of 3,3-disubstituted cyclopropenes with phosphines by a chiral lanthanocene catalyst bearing the C -symmetric 5,6-dioxy-4,7-trans-dialkyl-substituted tetrahydroindenyl ligands. This protocol offers a selective and efficient route for the synthesis of a new family of chiral phosphinocyclopropane derivatives, featuring 100 % atom efficiency, good diastereo- and enantioselectivity, broad substrate scope, and no need for a directing group.
环丙烯与膦的不对称氢膦化反应备受关注且具有重要意义，但由于缺乏合适的催化剂，迄今为止该反应几乎未被探索。我们在此报道了一种带有 C 对称的 5,6 - 二氧基 - 4,7 - 反式二烷基取代四氢茚基配体的手性镧系茂催化剂，实现了 3,3 - 二取代环丙烯与膦的非对映和对映选择性氢膦化反应。该方法为合成一类新的手性膦基环丙烷衍生物提供了一条选择性高且高效的途径，具有 100%的原子利用率、良好的非对映和对映选择性、广泛的底物范围，并且无需导向基团。
