Divalent Ytterbium Complex-Catalyzed Homo- and Cross-Coupling of Primary Arylsilanes.

Author(s) Liu, X.; Xiang, L.; Louyriac, E.; Maron, L.; Leng, X.; Chen, Y.
Journal J Am Chem Soc
Date Published 2018 Dec 20

Redistribution of primary silanes through C‒Si and Si‒H bond cleavage and reformation provides a straightforward synthesis of secondary silanes, but the poor selectivity and low efficiency severely hinders the application of this synthetic protocol. Here, we show that a newly synthesized divalent ytterbium alkyl complex exhibits unprecedentedly high catalytic activity towards the selective redistribution of primary arylsilanes to secondary arylsilanes. More significantly, this complex also effectively catalyzes the cross-coupling between electronic-withdrawing substituted primary arylsilanes and electronic-donating substituted primary arylsilanes to secondary arylsilanes containing two different aryls. DFT calculation indicates that the reaction always involve the exothermic formation of a hypervalent silicon upon facile addition of PhSiH3 to the Yb‒E (E = C, H) bond. This hypervalent can easily either generate directly the Yb‒Ph complex, or indirectly through the formation of Yb‒H, that is the key complex for the formation of Ph2SiH2.

DOI 10.1021/jacs.8b12138
ISSN 1520-5126
Citation J Am Chem Soc. 2018.

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