Stereodivergent asymmetric synthesis of P-atropisomeric Si-stereogenic monohydrosilanes

Abstract

We herein report an efficient one-pot strategy for the stereodivergent asymmetric synthesis of various P-atropisomeric Si-stereogenic monohydrosilanes with excellent stereoselectivity from dichlorosilanes.

X-type silyl ligands for transition-metal catalysis

“…In 2023, the He group developed an efficient one-pot method for the synthesis of a new type of Si-stereogenic monohydrosilanes with the BINEPINE skeleton (Scheme 35). 173 The key to this synthetic method is the tandem desymmetric substitution of dichloro-monohydrosilanes with chiral phosphine nucleophiles, followed by a stereospecific transformation. This one-pot process gives access to a wide range of functionalized enantioenriched P-atropisomeric Si-stereogenic monohydrosilanes 84 , featuring a rigid chiral environment and an easily modified Si-stereogenic centre, which could act as potential chiral silyl ligands in asymmetric catalysis.…”

“…In 2023, the He group discovered that the designed chiral PSiSi ligands could promote the Rh-catalyzed asymmetric hydrolytic oxidation of dihydrosilane 94 (Scheme 41). 173 Notably, using a pair of diastereomers L79 and L92 as the ligands, the enantioselectivities of the silanol product 95 are different, indicating that the chirality of the silicon atom has an important influence on stereocontrol. When a PSiS ligand L93 was employed in the reaction, a 99% yield of the corresponding silanol was obtained in 72% ee, which demonstrated the potential of these chiral silyl ligands to be applied in other catalytic asymmetric dehydrogenative reactions.…”