Stereospecific Si-C coupling and remote control of axial chirality by enantioselective palladium-catalyzed hydrosilylation of maleimides

• Published in: Nature communications Vol. 11; no. 1; pp. 2904 - 9
• Main Authors: Gu, Xing-Wei, Sun, Yu-Li, Xie, Jia-Le, Wang, Xing-Ben, Xu, Zheng, Yin, Guan-Wu, Li, Li, Yang, Ke-Fang, Xu, Li-Wen
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 09.06.2020; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 49/98; 631/154/309/2132/605; 639/638/549/972; 639/638/911/406/938; Activated carbon; Alkenes; Asymmetry; Carbon; Carbonyl compounds; Carbonyls; Catalysts; Chemical bonds; Chirality; Construction; Coupling; Enantiomers; Humanities and Social Sciences; Hydrosilylation; Isomerization; multidisciplinary; Organic chemistry; Organosilicon compounds; Palladium; Reduction; Remote control; Science; Science (multidisciplinary); Stereoselectivity; Succinimides
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-16716-5

Hydrosilylation of unsaturated carbon-carbon bonds with hydrosilanes is a very important process to access organosilicon compounds and ranks as one of the most fundamental reactions in organic chemistry. However, catalytic asymmetric hydrosilylation of activated alkenes and internal alkenes has proven elusive, due to competing reduction of carbon-carbon double bond or isomerization processes. Herein, we report a highly enantioselective Si-C coupling by hydrosilylation of carbonyl-activated alkenes using a palladium catalyst with a chiral TADDOL-derived phosphoramidite ligand, which inhibits O-hydrosilylation/olefin reduction. The stereospecific Si-C coupling/hydrosilylation of maleimides affords a series of silyl succinimides with up to 99% yield, >99:1 diastereoselectivity and >99:1 enantioselectivity. The high degree of stereoselectivity exerts remote control of axial chirality, leading to functionalized, axially chiral succinimides which are versatile building blocks. The product utility is highlighted by the enantioselective construction of N-heterocycles bearing up to three stereocenters. Catalytic asymmetric hydrosilylation of internal alkenes has proven elusive due to more favourable double bond reduction or isomerization. Here, the authors show an enantioselective Si-C coupling by hydrosilylation of activated alkenes using a palladium/phosphoramidite catalyst affording axially chiral succinimides.