化学
对映选择合成
催化作用
均分解
苯乙烯
非共价相互作用
催化循环
手性(物理)
钒
烯烃纤维
药物化学
甲烷氧化偶联
立体化学
光化学
激进的
有机化学
分子
氢键
聚合物
物理
夸克
量子力学
手征对称破缺
Nambu–Jona Lasinio模型
共聚物
作者
Chien-Tien Chen,Yu-Cheng Su,Chia-Hao Lu,Chien-I Lien,Shiang-Fu Hung,Chan-Wei Hsu,Rachit Agarwal,Ramuasagar Modala,Hung-Min Tseng,Pin-Xuan Tseng,Ryoma Fujii,Kyohei Kawashima,Susumu Mori
标识
DOI:10.1021/acscatal.1c01813
摘要
Asymmetric three-component 1,2-oxytrifluoromethylations of styrenes were explored by using N-oxyphthalimide (NOPI) as the resulting benzylic radical anchor after cross-coupling by a CF3 radical under the catalyses of chiral N-salicylidene-derived oxovanadium(V) complexes. Among the 15 different solvents and 15 different catalysts examined, the best scenarios were in i-PrOH with C3-tert-butyl or C3-fluoro-/2,5-dimethylphenyl-substituted vanadyl catalysts that led to the corresponding complementary S and R products in up to 88% yields and 87/86% ees, respectively, with further enrichment to at least 94% ee after a single recrystallization. The ccontrol α-(2-phenylcyclopropyl)styrene was tested to prove the asymmetric event involving the benzylic radical species. DFT computations showed that the SOMO of the benzylic radical is placed in a way to orient the CF3CH2 group away from the tert-butyl group in the salicylidene-l-tert-butylglycinate template by interacting with the N-oxygen atom of NOPI bound to the vanadium center with a bimolecular homolytic substitution (SH2) type mechanism. The enantioselectivity profile was dominated by several noncovalent interactions between the intermediary vanadium(NOPI) complex and the resulting benzylic radical.
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