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Reaction of Nitrogen‐Radicals with Organometallics Under Ni‐Catalysis: N‐Arylations and Amino‐Functionalization Cascades
Author(s) -
Angelini Lucrezia,
Davies Jacob,
Simonetti Marco,
Malet Sanz Laia,
Sheikh Nadeem S.,
Leonori Daniele
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201900510
Subject(s) - chemistry , radical , nucleophile , aryl , electrophile , organosilicon , intramolecular force , alkylation , cascade reaction , combinatorial chemistry , reactivity (psychology) , annulation , organic chemistry , catalysis , photochemistry , alkyl , medicine , alternative medicine , pathology
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.