Rhodium-Catalyzed (Asymmetric) Annulation of Silacyclobutanes with Bicyclic Olefins via C–Si Bond Activation DOI
Shengbo Xu, Fen Wang, Xingwei Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17453 - 17459

Published: Nov. 12, 2024

The carbon-to-silicon switch gives rise to silacycles that offer eminent biological and photophysical properties. Access chiral silacycles, especially midsized ones, via intermolecular coupling remains a considerable challenge due limited synthetic methods. Herein, rhodium(I)-catalyzed annulations between benzosilacyclobutenes (SCBs) bicyclic olefins are presented. A series of stable seven-membered have been accessed in high enantioselectivity the enantioselective [4 + 3] annulation SCBs 7-oxabenzonorbornadienes formal [2σ 2σ] C–C O–Si coupling. mechanism has investigated, where C–Si oxidative addition SCB established as turnover-limiting step.

Language: Английский

Tunable Regiodivergent Reactivity of N-Allenamides with Silacyclobutanes via Palladium Catalysis in the Synthesis of Silacyclic β-Aminosilanes DOI
Yidong Wang, Yan Sun, Tianying Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(14), P. 10882 - 10892

Published: July 4, 2024

The key structure of β-aminosilanes has attracted significant interest because their latent biological activities in the field medicinal chemistry. However, structural variety been significantly constrained by absence a comprehensive synthetic approach. Thus, development regiodivergent catalytic systems for construction structurally diverse via an intermolecular cycloaddition strategy would represent addition to limited toolkit available synthesis. We herein present attractive approach synthesis through regioselective N-allenamides with expansion silacyclobutanes catalyzed Pd/PR3. Just selecting suitable protecting group N-allenamides, regioselectivity is completely switched efficiently provide two regioisomers silacyclic β-aminosilanes. Two regioselectivities were proceeded during migratory insertion and reductive elimination process, origin which could be well rationalized using density functional theory calculations.

Language: Английский

Citations

6
Palladium-catalyzed double activation of Si-C(sp3) bond of benzosilacyclobutenes synergized with unexpected olefin migration and ring-opening hydrolysis DOI

Wen-Jing Shang,

Jia-Wei Si,

Junhui Zhu

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 440, P. 115788 - 115788

Published: Oct. 10, 2024

Language: Английский

Citations

2
Rhodium-Catalyzed (Asymmetric) Annulation of Silacyclobutanes with Bicyclic Olefins via C–Si Bond Activation DOI
Shengbo Xu, Fen Wang, Xingwei Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17453 - 17459

Published: Nov. 12, 2024

The carbon-to-silicon switch gives rise to silacycles that offer eminent biological and photophysical properties. Access chiral silacycles, especially midsized ones, via intermolecular coupling remains a considerable challenge due limited synthetic methods. Herein, rhodium(I)-catalyzed annulations between benzosilacyclobutenes (SCBs) bicyclic olefins are presented. A series of stable seven-membered have been accessed in high enantioselectivity the enantioselective [4 + 3] annulation SCBs 7-oxabenzonorbornadienes formal [2σ 2σ] C–C O–Si coupling. mechanism has investigated, where C–Si oxidative addition SCB established as turnover-limiting step.

Language: Английский

Citations

2