Rhodium‐Catalyzed Intramolecular C−H Silylation by Silacyclobutanes. Issue 21 (13th April 2016)

• Record Type: Journal Article
• Authors: Zhang, Qing‐Wei; An, Kun; Liu, Li‐Chuan; Guo, Shuangxi; Jiang, Chenran; Guo, Huifang; He, Wei
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 21(2016)
• Page Start: 6319
• Page End: 6323
• Publication Date: 2016-04-13
• Subjects: C−H activation -- metallocycle -- silole -- silylation -- β-hydrogen elimination; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201602376
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Silacyclobutane was discovered to be an efficient C−H bond silylation reagent. Under the catalysis of Rh I /TMS‐segphos, silacyclobutane undergoes sequential C−Si/C−H bond activations, affording a series of π‐conjugated siloles in high yields and regioselectivities. The catalytic cycle was proposed to involve a rarely documented endocyclic β‐hydride elimination of five‐membered metallacycles, which after reductive elimination gave rise to a Si−Rh I species that is capable of C−H activation. Abstract : Old reagent, new reactivity : Silacyclobutane was discovered to be an efficient C−H bond silylation reagent under the catalysis of Rh/TMS‐segophos. This new reactivity was attributed to a key Si−Rh I intermediate formed through a Si−C activation, endocyclic β‐H elimination and reductive elimination cascade. A wide array of siloles was obtained in high yields and excellent regioselectivities.