Lardy Samuel W, Schmidt Valerie A
Department of Chemistry and Biochemistry , University of California, San Diego , La Jolla , California 92093 , United States.
J Am Chem Soc. 2018 Oct 3;140(39):12318-12322. doi: 10.1021/jacs.8b06881. Epub 2018 Sep 20.
An intermolecular anti-Markovnikov hydroamination of alkenes has been developed using triethyl phosphite and N-hydroxyphthalimide. The process tolerates a wide range of alkenes, including vinyl ethers, silanes, and sulfides as well as electronically unbiased terminal and internal alkenes. The resultant N-alkylphthalimides can readily be transformed to the corresponding primary amines. Mechanistic probes indicate that the process is mediated via a phosphite promoted radical deoxygenation of N-hydroxyphthalimide to access phthalimidyl radicals.
利用亚磷酸三乙酯和N-羟基邻苯二甲酰亚胺，已开发出一种烯烃的分子间反马氏规则氢胺化反应。该反应过程可耐受多种烯烃，包括乙烯基醚、硅烷和硫化物，以及电子中性的末端和内烯烃。所得的N-烷基邻苯二甲酰亚胺可很容易地转化为相应的伯胺。机理研究表明，该过程是通过亚磷酸酯促进N-羟基邻苯二甲酰亚胺的自由基脱氧反应生成邻苯二甲酰亚胺基自由基来介导的。
