Synthesis of Bis-Cycloborate Olefin and Butatriene Derivatives through the Reduction of Alkynyl-Bridged Diboryl Compounds

• Published in: Inorganic chemistry Vol. 57; no. 20; pp. 12552 - 12561
• Main Authors: Zhao, Jinyu, Ru, Chenglong, Bai, Yunfei, Wang, Xingyong, Chen, Wenhao, Wang, Xi, Pan, Xiaobo, Wu, Jincai
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.10.2018
• ISSN: 0020-1669; 1520-510X; 1520-510X
• DOI: 10.1021/acs.inorgchem.8b01555

A series of bis-cycloborate olefin and butatriene derivatives were synthesized from alkynyl-bridged diboryl compounds using a simple reduction strategy. In the reduction route of 1,2-bis­[2-(dimesitylboranyl)­phenyl]­ethyne (1), bis-cycloborate olefin (4) to diborate-bridged stilbene (5) can be obtained selectively by varying the reaction temperature. In addition, a thermal isomerization from 4 to 5 was found as a result of the rearrangement of double bonds. The generality of this reaction was further verified in similar reduction reactions. In the direduction of 1,2-bis­[8-(dimesitylboranyl)­naphthalen-1-yl]­ethyne (2), the bis-cycloborate olefin (6) was isolated in high yield and demonstrated no thermal isomerization. In the two-electron reduction of 1,8-bis­{[2-(dimesitylboranyl)­phenyl]­ethynyl}­naphthalene (3), the bis-cycloborate butatriene (7) was obtained unexpectedly because of the departure of the naphthyl group. When using Na as the reductant and diethyl ether as the solvent, 1,2-bis­[(Z)-2-(dimesitylboranyl)­benzylidene]-1,2-dihydroacenaphthylene (8) was isolated after adding 1 or 2 drops of H2O to the reduction reaction filtrates. Meanwhile, the related mechanisms for radical cyclization, thermal isomerization, and formation of bis-cycloborate butatriene were also discussed.