Rhodium‐Catalyzed Synthesis of Chiral Monohydrosilanes by Intramolecular C−H Functionalization of Dihydrosilanes. (23rd December 2020)

• Record Type: Journal Article
• Authors: Ma, Wenpeng; Liu, Li‐Chuan; An, Kun; He, Tao; He, Wei
• Is Part Of: Angewandte Chemie. Volume 133:Number 8(2021)
• Page Start: 4291
• Page End: 4297
• Publication Date: 2020-12-23
• Subjects: desymmetrization -- dihydrosilanes -- enantioselectivity -- monohydrosilane -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202013041
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The preparation of chiral monohydrosilanes remains a rarely achieved goal. To this end a Rh‐catalyzed desymmetrization of dihydrosilanes by way of intramolecular C(sp 2 )−H functionalization under simple and mild conditions has now been developed. This method provides easy access to a broad range of chiral monohydrosilanes in good yields with excellent enantioselectivities (up to >99 % ee ). The resulting monohydrosilanes constitute a good platform to access stereogenic silicon compounds, as well as useful compounds to probe silicon stereochemistry. Abstract : A Rh‐chiral diphosphine complex was found to catalyze desymmetrization of dihydrosilanes by formal intramolecular Si−H/C−H dehydrogenative coupling reactions. This simple, mild, and practical method results in unprecedently high enantioselectivity and a broad substrate scope. The chiral monohydrosilanes could be further elaborated into various stereogenic silicon compounds in a stereospecific manner.