美国加州大学Ohyun Kwon团队报道了氨基脱烯基化，臭氧分解和铜催化将C(sp³)–C(sp²)键转化为C(sp³)–N键。相关研究成果发表在2023年8月25日出版的国际知名学术期刊《科学》。

烯烃π键的胺化已经开展了大量研究。相反，相邻的C（sp³）–C（sp²）σ键的类似功能化要少得多。

该文中，研究人员报道了臭氧分解和铜催化如何在温和的反应条件下使烯烃C（sp³）–C（sp²）σ键断裂交叉偶联反应能够构建新的C（sp³）–N键。研究人员将这种非常规转化用于激素、药物试剂、肽和核苷的后期修饰。此外，海将大量可用的萜烯和萜类化合物与氮亲核试剂偶联，以获得人工萜类生物碱和复杂的手性胺。

此外，研究人员应用商品化学品α-甲基苯乙烯作为甲基化试剂，在一个合成步骤中直接从经典核苷制备甲基化核苷。机理研究揭示了一种不寻常的铜离子对协同过程。

附：英文原文

Title: Aminodealkenylation: Ozonolysis and copper catalysis convert C(sp3)–C(sp2) bonds to C(sp3)–N bonds

Author: Zhiqi He, Jose Antonio Moreno, Manisha Swain, Jason Wu, Ohyun Kwon

Issue&Volume: 2023-08-25

Abstract: Great efforts have been directed toward alkene π bond amination. In contrast, analogous functionalization of the adjacent C(sp3)–C(sp2) σ bonds is much rarer. Here we report how ozonolysis and copper catalysis under mild reaction conditions enable alkene C(sp3)–C(sp2) σ bond–rupturing cross-coupling reactions for the construction of new C(sp3)–N bonds. We have used this unconventional transformation for late-stage modification of hormones, pharmaceutical reagents, peptides, and nucleosides. Furthermore, we have coupled abundantly available terpenes and terpenoids with nitrogen nucleophiles to access artificial terpenoid alkaloids and complex chiral amines. In addition, we applied a commodity chemical, α-methylstyrene, as a methylation reagent to prepare methylated nucleosides directly from canonical nucleosides in one synthetic step. Our mechanistic investigation implicates an unusual copper ion pair cooperative process.

DOI: 10.1126/science.adi4758

Source: https://www.science.org/doi/full/10.1126/science.adi4758