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

• 成果类型: Article
• 署名作者: He, Zhiqi; Moreno, Jose Antonio; Swain, Manisha; Wu, Jason; Kwon, Ohyun
• 署名单位: University of California System; University of California Los Angeles
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12921
• DOI: 10.1126/science.adi4758
• 发表日期: 2023-08-25
• 页码: 877-885
• 关键词: ligand-substitution-reactions; transition-metal-complexes; hydrogen-peroxide; alkyl radicals; electron-transfer; exchange reactions; c-n; kinetics; oxidation; amines

摘要

Great efforts have been directed toward alkene p bond amination. In contrast, analogous functionalization of the adjacent C(sp(3))-C(sp(2)) s bonds is much rarer. Here we report how ozonolysis and copper catalysis under mild reaction conditions enable alkene C(sp(3))-C(sp(2)) s bond-rupturing cross-coupling reactions for the construction of new C(sp(3))-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, a-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.