TY - JOUR
T1 - Cyclic (Alkyl)(Amino)Carbene-Iminoboryl Compounds with Three Formal Oxidation States
AU - Mao, Xiaofeng
AU - Qiu, Shuang
AU - Guo, Rui
AU - Dai, Yuyang
AU - Zhang, Jie
AU - Kong, Lingbing
AU - Xie, Zuowei
N1 - Funding information:
L.K. gratefully acknowledges financial support from the National Natural Science Foundation of China (22271174), the Taishan Scholar Project of Shandong Province of China (tsqn202211007), the natural Science Foundation of Shandong Province (ZR2019ZD46), and the Multidisciplinary Research and Innovation Team of Young Scholars of Shandong University (2020QNQT007). Z.X. thanks the Research Grants Council of HKSAR (Project no. 14307421) and the Southern University of Science and Technology for financial support.
Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/4/17
Y1 - 2024/4/17
N2 - BN/CC isosterism is an effective strategy to build hybrid functional molecules with unique properties. In contrast to the alkynyl iminium salts derived from cyclic (alkyl)(amino)carbenes (CAACs) that feature only one reversible reduction wave, the isoelectronic cationic CAAC-iminoboryl adducts could be singly and doubly reduced smoothly. Both the resultant neutral radical and anionic azaborataallenes bear NBC-mixed allenic structures. The former radical has a high spin-density of 0.55e at CCAAC carbon, yet exhibits formal boron-centered radical reactivity. The latter azaborataallenes feature the nucleophilic CCAAC center and polar N(δ-)═B(δ+)═C(δ-) unit, and readily undergo nucleophilic substitution, isocyanide insertion, dipolar addition and cycloaddition reactions etc. The N-substituents have been shown to have a significant influence on the solid-state structure, thermal stability, and reactivity of azaborataallenes. This work showcases the allenic BN-unsaturated species as versatile building blocks in organic synthesis.
AB - BN/CC isosterism is an effective strategy to build hybrid functional molecules with unique properties. In contrast to the alkynyl iminium salts derived from cyclic (alkyl)(amino)carbenes (CAACs) that feature only one reversible reduction wave, the isoelectronic cationic CAAC-iminoboryl adducts could be singly and doubly reduced smoothly. Both the resultant neutral radical and anionic azaborataallenes bear NBC-mixed allenic structures. The former radical has a high spin-density of 0.55e at CCAAC carbon, yet exhibits formal boron-centered radical reactivity. The latter azaborataallenes feature the nucleophilic CCAAC center and polar N(δ-)═B(δ+)═C(δ-) unit, and readily undergo nucleophilic substitution, isocyanide insertion, dipolar addition and cycloaddition reactions etc. The N-substituents have been shown to have a significant influence on the solid-state structure, thermal stability, and reactivity of azaborataallenes. This work showcases the allenic BN-unsaturated species as versatile building blocks in organic synthesis.
UR - https://www.scopus.com/pages/publications/85189915255
U2 - 10.1021/jacs.4c01934
DO - 10.1021/jacs.4c01934
M3 - Journal article
C2 - 38587904
AN - SCOPUS:85189915255
SN - 0002-7863
VL - 146
SP - 10917
EP - 10924
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 15
ER -