We report herein that a highly regioselective silicon-carbon bond-forming silylation of unsymmetric gem-difluorocyclopropenes based on Si-C or Si-B bond cleavage of organosilicon reagents was achieved using palladium or copper catalysis...
Transition-metal-catalyzed silicon-carbon bond-forming silylation is one of the most important processes and remains an ongoing challenge in both organosilicon chemistry and homogeneous catalysis. Herein we report an unprecedent and convenient...
Strategies on the construction of enantiomerically pure silicon‐stereogenic silanes generally relies on desymmetrization of prochiral and symmetric substrates. However, dynamic kinetic asymmetric transformations of organosilicon compounds have remained underdeveloped and unforeseen owing to a lack of an effective method for deracemization of the static silicon stereocenters. Here we report the first Rh‐catalyzed dynamic kinetic asymmetric intramolecular hydrosilylation (DyKAH) with “silicon‐centered” racemic hydrosilanes that enables the facile preparation of silicon‐stereogenic benzosiloles in good yields and excellent enantioselectivities. The special rhodium catalyst controlled by non‐diastereopure‐type mixed phosphine‐phosphoramidite ligand with axial chirality and multiple stereocenters can induce enantioselectivity efficiently in this novel DyKAH reaction. Density functional theory (DFT) calculations suggest that the amide moiety in chiral ligand plays important role in facilitating the SN2 substitution of chloride ion to realize the chiral inversion of silicon center.
Catalytic asymmetric hydrosilylation is an extremely important and atom-economical chemical transformation in the field of catalysis and synthetic chemistry. Although stereospecific hydrosilylation provides a general strategy for elaborating diastereo- and...
Given the powerful potentials of chiral-at-silicon chemistry, enantioselective synthesis of Si-stereogenic center has attracted substantial research interest in recent years. However, the catalytic asymmetric synthesis of Si-stereogenic organosilicon compounds remains...
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