DFT study of Ni/NHC-catalyzed C–H alkylation of fluoroarenes with alkenes to synthesize fluorotetralins: mechanism, chemoselectivity of C–H vs. C–F bond activation, and regio- and enantioselectivities of C–H bond activation

Abstract

Density functional theory calculations have been carried out to elucidate the mechanism, enantio-, regio-, and chemoselectivities, and the role of NHC ligand in the Ni/NHC-catalyzed alkylation of fluoroarenes with alkenes,...

Recent Advances in Cycloaddition Reactions of Donor-Acceptor Aziridines via Carbon-Carbon Bond Cleavage

“…底物扩展研究 表明, 如果把芳基炔醇换成芳基炔胺或者 4-戊炔醇时, 这类化合物和 D-A 氮杂环丙烷的不对称环加成反应不 能发生(Scheme 20). [4][5]7] 、 富电子炔烃化合物 [8] 捕获, 生 成相应的环化产物. 此外, D-A 氮杂环丙烷和两种不同 芳香醛的竞争反应实验也验证了亚胺叶立德中间体是 亲电性的, 因为苯甲醛反应活性比对氯苯甲醛的反应活 性高 [28]…”

“…最近, 罗永春/徐鹏飞小组 [7] 实现了在 Sc(OTf) 3 催化 下, D-A 氮杂环丙烷和糖类化合物衍生的手性烯烃的 [3＋2]环加成反应, 构建了一系列手性含氮螺糖苷骨架, 这类骨架具有广泛的药理作用. 比如螺旋藻苷衍生物在 检测抗病毒和抗癌药物方面具有临床价值(Scheme 6).…”

A Theoretical Study on the 1,2-Bis-Silylation of Internal Alkynes Catalyzed by Ni-NHC: Understanding the Influential Factors on Catalyst Conversion, Stability, and Reactivity

“…In recent years, there has been a surge in mechanistic studies focusing on specific Ni-NHC-catalyzed reactions. For instance, in 2015, Wu and colleagues delved into the Ni-NHC-catalyzed hydrogenolysis of aryl ethers under both acid and base conditions.…”

Exploring a general mechanistic map on NHC-catalyzed activation/transformation reactions of saturated carboxylic anhydrides

“…Herein, a theoretical study of the title reaction has been performed using density functional theory, which has proved to be a powerful method for elucidating the mechanisms of organocatalytic 14 and organometallic reactions. 15 In this study, we intend to disclose a general mechanistic map for saturated carboxylic anhydride activation/transformation, verify the aforementioned hypothesis, and explore the key factors that control the stereoselectivity.…”