Borane-Catalyzed Cross-Metathesis Strategy for Facile Transformation of Cyclic (Alkyl)(Amino)Germylenes

Bin Rao; Liliang Wang; Rei Kinjo

doi:10.1002/anie.201811574

Borane-Catalyzed Cross-Metathesis Strategy for Facile Transformation of Cyclic (Alkyl)(Amino)Germylenes

Bin Rao, Liliang Wang, Rei Kinjo^*

^*Corresponding author for this work

Nanyang Technological University

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

A borane B(C₆F₅)₃-catalyzed metathesis reaction between the Si−C bond in the cyclic (alkyl)(amino)germylene (CAAGe) 1 and the Si−H bond in a silane (R₃SiH; 2) is reported. Mechanistic studies propose that the initial step of the reaction involves Si−H bond activation to furnish an ionic species [1-SiR₃]⁺[HB(C₆F₅)₃]⁻, from which [Me₃Si]⁺[HB(C₆F₅)₃]⁻ and an azagermole intermediate are generated. The former yields Me₃SiH concomitant with the regeneration of B(C₆F₅)₃ whereas the latter undergoes isomerization to afford CAAGes bearing various silyl groups on the carbon atom next to the germylene center. This strategy allows the straightforward synthesis of eight new CAAGes starting from 1.

Original language	English
Pages (from-to)	231-235
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	1
DOIs	https://doi.org/10.1002/anie.201811574
Publication status	Published - Jan 2 2019
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ASJC Scopus Subject Areas

Catalysis
General Chemistry

Keywords

borane
cross-metathesis
germylene
reaction mechanisms
structure elucidation

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title = "Borane-Catalyzed Cross-Metathesis Strategy for Facile Transformation of Cyclic (Alkyl)(Amino)Germylenes",

abstract = "A borane B(C6F5)3-catalyzed metathesis reaction between the Si−C bond in the cyclic (alkyl)(amino)germylene (CAAGe) 1 and the Si−H bond in a silane (R3SiH; 2) is reported. Mechanistic studies propose that the initial step of the reaction involves Si−H bond activation to furnish an ionic species [1-SiR3]+[HB(C6F5)3]−, from which [Me3Si]+[HB(C6F5)3]− and an azagermole intermediate are generated. The former yields Me3SiH concomitant with the regeneration of B(C6F5)3 whereas the latter undergoes isomerization to afford CAAGes bearing various silyl groups on the carbon atom next to the germylene center. This strategy allows the straightforward synthesis of eight new CAAGes starting from 1.",

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author = "Bin Rao and Liliang Wang and Rei Kinjo",

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doi = "10.1002/anie.201811574",

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AU - Rao, Bin

AU - Wang, Liliang

AU - Kinjo, Rei

PY - 2019/1/2

Y1 - 2019/1/2

N2 - A borane B(C6F5)3-catalyzed metathesis reaction between the Si−C bond in the cyclic (alkyl)(amino)germylene (CAAGe) 1 and the Si−H bond in a silane (R3SiH; 2) is reported. Mechanistic studies propose that the initial step of the reaction involves Si−H bond activation to furnish an ionic species [1-SiR3]+[HB(C6F5)3]−, from which [Me3Si]+[HB(C6F5)3]− and an azagermole intermediate are generated. The former yields Me3SiH concomitant with the regeneration of B(C6F5)3 whereas the latter undergoes isomerization to afford CAAGes bearing various silyl groups on the carbon atom next to the germylene center. This strategy allows the straightforward synthesis of eight new CAAGes starting from 1.

AB - A borane B(C6F5)3-catalyzed metathesis reaction between the Si−C bond in the cyclic (alkyl)(amino)germylene (CAAGe) 1 and the Si−H bond in a silane (R3SiH; 2) is reported. Mechanistic studies propose that the initial step of the reaction involves Si−H bond activation to furnish an ionic species [1-SiR3]+[HB(C6F5)3]−, from which [Me3Si]+[HB(C6F5)3]− and an azagermole intermediate are generated. The former yields Me3SiH concomitant with the regeneration of B(C6F5)3 whereas the latter undergoes isomerization to afford CAAGes bearing various silyl groups on the carbon atom next to the germylene center. This strategy allows the straightforward synthesis of eight new CAAGes starting from 1.

KW - borane

KW - cross-metathesis

KW - germylene

KW - reaction mechanisms

KW - structure elucidation

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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ER -

Borane-Catalyzed Cross-Metathesis Strategy for Facile Transformation of Cyclic (Alkyl)(Amino)Germylenes

Abstract

Bibliographical note

ASJC Scopus Subject Areas

Keywords

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