CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2020 Apr 27;59(18):7057-7062. doi: 10.1002/anie.201916076. Epub 2020 Mar 11.
1,2-Bisphosphines have been identified as one class of important and powerful chiral ligands in asymmetric catalysis with transition metals. Herein, a copper(I)-catalyzed asymmetric hydrophosphination of α,β-unsaturated phosphine sulfides was developed with the assistance of "soft-soft" interaction between copper(I)-catalyst and the phosphine sulfide moiety, which afforded 1,2-bisphosphine derivatives with diversified electronic nature and steric hindrance in high to excellent yields with high to excellent enantioselectivity. Moreover, the challenging catalytic asymmetric hydrophosphination/protonation reaction was achieved with excellent enantioselectivity. Strikingly, the dynamic kinetic resolution of racemic diarylphosphines was also successfully carried out with high to excellent diastereo- and enantioselectivities. Interestingly, the nucleophilic copper(I)-diphenylphosphide species was characterized by P NMR spectrum and mass spectrum. At last, three products were transformed to chiral 1,2-bisphosphines, which were employed as ligands in Rh-catalyzed asymmetric hydrogenation of α-amino-α,β-unsaturated ester. The α-amino acid derivative was produced in high enantioselectivity, which demonstrated the utility of the present methodology.
1,2-双膦配体已被确定为一类在过渡金属不对称催化中具有重要和强大的手性配体。在此，在铜（I）-催化剂与膦硫醚部分之间的“软-软”相互作用的辅助下，开发了铜（I）-催化的α,β-不饱和膦硫醚的不对称氢膦化反应，以高至优异的收率和高至优异的对映选择性得到了具有多样化电子性质和空间位阻的 1,2-双膦衍生物。此外，还实现了具有优异对映选择性的挑战性催化不对称氢膦化/质子化反应。引人注目的是，外消旋二芳基膦的动态动力学拆分也以高至优异的非对映选择性和对映选择性成功进行。有趣的是，亲核铜（I）-二苯基膦物种通过 P NMR 光谱和质谱进行了表征。最后，三个产物被转化为手性 1,2-双膦配体，它们在 Rh 催化的α-氨基-α,β-不饱和酯的不对称氢化中被用作配体。高对映选择性地生成了α-氨基酸衍生物，证明了本方法的实用性。
