An unusualtrans-hydrosilylation of prochiral 1,1-disubstituted cyclopropenes revealing the different nature of asymmetric palladium and rhodium catalysis

Abstract

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...

Palladium‐Catalyzed Enantioselective Hydrofunctionalization of Alkenes: Recent Advances

“…In the same year, Xu, Li and coworkers developed a novel palladium‐catalyzed enantioselective hydrosilylation of 1,1‐disubstituted carbonyl cyclopropenes with dihydrophenylsilane using TADDOL‐derived phosphoramidite ( L12 ) as a chiral ligand (Scheme 11). [47] Various trans ‐type silylcyclopropanes were obtained in moderate yields with good diastereo‐ and enantio‐selectivities. Mechanism studies revealed that the spatial repulsion between chiral ligand ( L12 ) and substrates would be a key factor in achieving trans ‐type diastereospecific hydrosilylation.…”

An unusual autocatalysis with an air-stable Pd complex to promote enantioselective synthesis of Si-stereogenic enynes

“… 15 (2) A high level of stereoselectivity and regio- or chemoselectivity cannot be obtained because of the poor compatibility between silicon-center chirality and functional groups. 16 Considering the importance of the catalytic construction of functional silanes bearing a silicon-stereogenic center, we expect to further develop new reaction systems of catalytic asymmetric hydrosilylation, which can be applied to more types of functional alkynes. Notably, there is no report on the catalytic asymmetric synthesis of silicon-stereogenic enynes via hydrosilylation of 1,3-diynes.…”

Rapid Access to Chiral Spiro[2.3] Lactams: Stereoselective Hydroborylation and Hydrosilylation and Remote Control of Axial Chirality by Copper-Catalyzed Desymmetrization of Spirocyclopropenes

“…Recently, the desymmetrization strategy has been well developed and widely employed in asymmetric synthesis . For example, the diastereoselective and enantioselective hydroborylation and hydrosilylation of strained alkenes, including cyclopropenes , and cyclobutenes, , had been well established . Thus, the provided enantio-enriched boronic esters work as valuable synthetic building blocks, while the asymmetric hydrosilylation ranks as one of the most important reactions in organosilicon chemistry .…”