Reaction of Nitrogen-Radicals with Organometallics Under Ni-Catalysis: N-Arylations and Amino-Functionalization Cascades

被引：40

作者：

Angelina, Lucrezia ^{[1
]}

Davies, Jacob ^{[1
]}

Simonetti, Marco ^{[1
]}

Sanz, Laia Malet ^{[2
]}

Sheikh, Nadeem S. ^{[3
]}

Leonori, Daniele ^{[1
]}

机构：

[1] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs, England

[2] Eli Lilly & Co Ltd, Windelesham GU20 6PH, Surrey, England

[3] King Faisal Univ, Dept Chem, Coll Sci, POB 380, Al Hasa 31982, Saudi Arabia

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 15期

基金：

欧洲研究理事会; 英国工程与自然科学研究理事会;

关键词：

alkaloid; arylation; nitrogen radicals; radical cyclization; single electron transfer; ELECTROPHILIC AMINATION; ARYLBORONIC ACIDS; CARBON-NITROGEN; ARYL; PHOTOREDOX; GENERATION; AMIDYL; CYCLIZATIONS; MECHANISM; KINETICS;

D O I：

10.1002/anie.201900510

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein, we report a strategy for the generation of nitrogen-radicals by ground-state single electron transfer with organyl-Ni-I species. Depending on the philicity of the N-radical, two types of processes have been developed. In the case of nucleophilic aminyl radicals direct N-arylation with aryl organozinc, organoboron, and organosilicon reagents was achieved. In the case of electrophilic amidyl radicals, cascade processes involving intramolecular cyclization, followed by reaction with both aryl and alkyl organometallics have been developed. The N-cyclization-alkylation cascade introduces a novel retrosynthetic disconnection for the assembly of substituted lactams and pyrrolidines with its potential demonstrated in the short total synthesis of four venom alkaloids.

引用

页码：5003 / 5007

页数：5