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

Research output: Contribution to journalArticle

  • Authors:
  • Lucrezia Angelini
  • Jacob Davies
  • Marco Simonetti
  • Laia Malet Sanz
  • Nadeem S. Sheikh
  • And 1 others
  • External authors:
  • Daniele Leonori

Abstract

Here 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.

Bibliographical metadata

Original languageEnglish
Pages (from-to)5003-5007
Number of pages5
JournalAngewandte Chemie International Edition
Volume58
Issue number15
Early online date19 Feb 2019
DOIs
Publication statusPublished - 2019