卡宾
三氟甲基
分子内力
化学
键裂
分子
组合化学
劈理(地质)
催化作用
立体化学
药物化学
有机化学
材料科学
断裂(地质)
复合材料
烷基
作者
Xiaolong Zhang,Yongquan Ning,Zhaohong Liu,Shuang Li,Giuseppe Zanoni,Xihe Bi
标识
DOI:10.26434/chemrxiv-2022-5mcgj
摘要
The monofunctionalized carbodefluorination of readily accessible CF3 groups is acknowledged as an attractive approach to the preparation of partially fluorinated molecules. However, their defluorinative difunctionalization remains a challenging and unmet goal. Herein, we report an unprecedented defluorinative carboimination of trifluoromethyl ketones via a strategy of silver carbene-initiated rearrangement, in which both C–F bond and carbonyl group of the trifluoromethyl ketones were functionalized simultaneously, thus providing a straightforward synthetic method for medicinally relevant α,α-difluoroimines. The current approach involves a silver carbene-initiated intramolecular cascade process by integrating successive cleavage of C–F bond and formation of C–C and C=N bonds on a single molecule entity, which differs relevantly from the stepwise mechanism of reported carbodefluorination of CF3 groups. Mechanistic studies disclose that silver catalysis plays a critical role, particularly in the stages of C–F bond cleavage and aza-Claisen rearrangement.
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