Bifunctional Silylene–Aminoborane Enables Cooperative Activation of Unsaturated Bonds and Access to Heteroatom‐Enriched Polycycle

Z Zheng Su (Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China) M Mingdong Zhong (Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China) X Xixi Meng (Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China) R Ren Gao J Jiancheng Li (Department of Chemistry, College of Science) M Minyi Yuan (Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China) H Herbert W. Roesky (Institut für Anorganische Chemie Georg‐August‐Universität Göttingen Göttingen 37077 Germany) S Shaoguang Zhang (Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education) Department of Chemistry Tsinghua University Beijing 100084 China)

Abstract

Abstract We report the synthesis and cooperative reactivity of a bifunctional silylene–aminoborane compound, 1‐Ph‐2‐ t Bu‐1 H ‐2,1‐benzazaborolyl‐(amidinato)silylene ( 1 ), designed to preserve the ambiphilicity of both functional units while preventing intramolecular deactivation. 1 engages in unprecedented multicomponent activations of unsaturated bonds, including alkynes and phosphaalkynes, to construct novel main‐group element embedded polycyclic frameworks. Reaction with alkynes led to rare main‐group elements enriched semibullvalenes via highly regioselective [2 + 2 + 1] cycloaddition. Notably, reaction with a phosphaalkyne induced a distinct S N Ar‐like B─C bond cleavage and formation of a B─N─Si─P‐embedded barrelene analogue. Structural and computational analyses revealed the synergistic multi‐site activation modes and reaction pathways.

Article Details

Volume / Issue Vol. 64, Issue 45
Published November 03, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (8)

Z

Zheng Su

Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China

M

Mingdong Zhong

Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China

X

Xixi Meng

Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China

R

Ren Gao

J

Jiancheng Li

Department of Chemistry, College of Science

M

Minyi Yuan

Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin 300387 China

H

Herbert W. Roesky

Institut für Anorganische Chemie Georg‐August‐Universität Göttingen Göttingen 37077 Germany

S

Shaoguang Zhang

Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education) Department of Chemistry Tsinghua University Beijing 100084 China