Nickel‐Catalyzed Reductive C(sp2)−Si Coupling of Chlorohydrosilanes via Si−Cl Cleavage. (21st March 2022)

• Record Type: Journal Article
• Authors: Zhao, Zhen‐Zhen; Pang, Xiaobo; Wei, Xiao‐Xue; Liu, Xue‐Yuan; Shu, Xing‐Zhong
• Is Part Of: Angewandte Chemie. Volume 134:Number 21(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-21
• Subjects: Hydrosilanes -- Nickel -- Organosilanes -- Silylation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202200215
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: We report here a new method for the synthesis of organohydrosilanes from phenols and ketones. This method is established through reductive C−Si coupling of chlorohydrosilanes via unconventional Si−Cl cleavage. The reaction offers access to aryl‐ and alkenylhydrosilanes with a scope that is complementary to those of the established methods. Electron‐rich, electron‐poor, and ortho ‐/ meta ‐/ para ‐substituted (hetero)aryl electrophiles, as well as cyclic and acyclic alkenyl electrophiles, were coupled successfully. Functionalities, including Grignard‐sensitive groups (e.g., primary amine, amide, phenol, ketone, ester, and free indole), acid‐sensitive groups (e.g., ketal and THP protection), alkyl‐Cl, pyridine, furan, thiophene, Ar‐Bpin, and Ar‐SiMe3, were tolerated. Gram‐scale reaction, incorporation of ‐Si(H)R2 into complex biologically active molecules, and derivatization of formed organohydrosilanes are demonstrated. Abstract : A new C−Si bond‐forming reaction between R−X and Cl−Si(H)R2 was achieved using reductive nickel catalysis. This method offers access to structurally diverse aryl‐ and alkenylhydrosilanes from phenol and ketone derivatives. The reaction can be conducted on gram scale and allows for incorporating a hydrosilane moiety into biologically active molecules.