Construction of Chiral Tetraorganosilicons by Tandem Desymmetrization of Silacyclobutanes/Intermolecular Dehydrogenative Silylation. Issue 4 (19th December 2016)

• Record Type: Journal Article
• Authors: Zhang, Qing‐Wei; An, Kun; Liu, Li‐Chuan; Zhang, Qi; Guo, Huifang; He, Wei
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 4(2017)
• Page Start: 1125
• Page End: 1129
• Publication Date: 2016-12-19
• Subjects: dibenzosiloles -- enantioselectivity -- silacyclobutanes -- tetraorganosilicons; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201609022
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We report a method to construct chiral tetraorganosilicons by tandem silacyclobutane (SCB) desymmetrization–dehydrogenative silylations. A wide array of dibenzosiloles with stereogenic quaternary silicon centers were obtained in good yields and enantioselectivities up to 93 % ee . Chiral TMS‐segphos was found to be a superior ligand in terms of reactivity and enantioselectivity. Abstract : Chiral silicon : A Rh‐catalyzed reaction between silacyclobutane and (hetero)arenes in the presence of ( R )‐ or ( S )‐TMS‐segphos provides access to a wide array of chiral dibenzosiloles in good yields and enantioselectivities (up to 93 % ee ). The reaction proceeds through a rarely documented desymmetrization of silacyclobutane, followed by intra‐ and intermolecular dehydrogenative silylation processes.