Construction of Chiral Tetraorganosilicons by Tandem Desymmetrization of Silacyclobutanes/Intermolecular Dehydrogenative Silylation

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...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2017-01, Vol.56 (4), p.1125-1129
Main Authors: Zhang, Qing‐Wei, An, Kun, Liu, Li‐Chuan, Zhang, Qi, Guo, Huifang, He, Wei
Format: Article
Language:English
Subjects:
Construction methods
Dehydrogenation
dibenzosiloles
Enantiomers
enantioselectivity
silacyclobutanes
tetraorganosilicons
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Summary: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. 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.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201609022