Comprehensive Summary A novel method for synthesizingα-oxygen organoboron compounds has been developed through acylsilane-based carbene insertion reactions into C—B bonds.As coupling partners,readily available organ...Comprehensive Summary A novel method for synthesizingα-oxygen organoboron compounds has been developed through acylsilane-based carbene insertion reactions into C—B bonds.As coupling partners,readily available organoboron compounds(alkenyl,allyl,and allenyl B(pin))were employed.Based on the substrates,pure insertion into C—B bonds or insertion followed by a siloxy group rearrangement process(from carbon to boron)would occur,delivering theα-oxygen organoboron compounds with great diversities.Control experiments demonstrated that the electronic effect of the substituents mainly controlled the rearrangement process.Besides,no matter which isomer of substrate(Z or E)was used,the reaction withβ-aryl-substituted alkenyl B(pin)affords both isomers of products(Z and E,separable through column chromatography).Trapping experiments indicated the triplet energy transfer process was involved.展开更多
基金supported by the National Natural Science Foundation of China(22101261)the Natural Science Foundation of Henan Province(232300421087,232301420045)the Zhengzhou University of China(2023ZZUJGXM168).
文摘Comprehensive Summary A novel method for synthesizingα-oxygen organoboron compounds has been developed through acylsilane-based carbene insertion reactions into C—B bonds.As coupling partners,readily available organoboron compounds(alkenyl,allyl,and allenyl B(pin))were employed.Based on the substrates,pure insertion into C—B bonds or insertion followed by a siloxy group rearrangement process(from carbon to boron)would occur,delivering theα-oxygen organoboron compounds with great diversities.Control experiments demonstrated that the electronic effect of the substituents mainly controlled the rearrangement process.Besides,no matter which isomer of substrate(Z or E)was used,the reaction withβ-aryl-substituted alkenyl B(pin)affords both isomers of products(Z and E,separable through column chromatography).Trapping experiments indicated the triplet energy transfer process was involved.
