Enantioselective Rhodium-Catalyzed Desymmetric Hydrosilylation of Cyclopropenes

Catalytic hydrosilylation
of alkenes ranks as one of the most important
academic and industrial synthetic reactions in homogeneous catalysis
and organosilicon chemistry. In this work, a highly enantioselective
Rh-catalyzed desymmetric hydrosilylation reaction of 1,1-disubstituted
cyclopropenes with the promotion of chiral DTBM-SEGPHOS is described.
It allows for a straightforward access to potentially valuable chiral
organosilicon compounds bearing a carbon quaternary stereocenter in
high yields with good diastereo- and enantioselectivities (up to >99:1
d.r. and >99% ee) in a 100% atom-efficient manner from readily
available
starting cyclopropenes and hydrosilanes.

烯烃的催化氢化硅基化反应，是均相催化与有机硅化学领域中最为重要的学术及工业合成反应之一。本工作报道了在手性DTBM-SEGPHOS配体促进下，铑催化的1,1-二取代环丙烯的高对映选择性去对称化氢化硅基化反应。该反应以易得的环丙烯与氢硅烷为起始原料，以100%原子经济性的方式，可直接获得带有碳季碳立体中心的高价值手性有机硅化合物，反应产率优异，非对映选择性比值（d.r.）与对映体过量值（ee）俱佳，最高可达>99:1的d.r.与>99%的ee。