Formamides as Isocyanate Surrogates: A Mechanistically Driven Approach to the Development of Atom-Efficient, Selective Catalytic Syntheses of Ureas, Carbamates, and Heterocycles

Jeffrey Bruffaerts, Niklas Von Wolff, Yael Diskin-Posner, Yehoshoa Ben-David, David Milstein

Research output: Contribution to journalArticle

Abstract

Despite the hazardous nature of isocyanates, they remain key building blocks in bulk and fine chemical synthesis. By surrogating them with less potent and readily available formamide precursors, we herein demonstrate an alternative, mechanistic approach to selectively access a broad range of ureas, carbamates, and heterocycles via ruthenium-based pincer complex catalyzed acceptorless dehydrogenative coupling reactions. The design of these highly atom-efficient procedures was driven by the identification and characterization of the relevant organometallic complexes, uniquely exhibiting the trapping of an isocyanate intermediate. Density functional theory (DFT) calculations further contributed to shed light on the remarkably orchestrated chain of catalytic events, involving metal-ligand cooperation.

Original languageEnglish
Pages (from-to)16486-16493
Number of pages8
JournalJournal of the American Chemical Society
Volume141
Issue number41
DOIs
Publication statusPublished - Oct 16 2019

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Formamides
Isocyanates
Carbamates
Organometallics
Ruthenium
Urea
Density functional theory
Ligands
Atoms
Metals

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Formamides as Isocyanate Surrogates : A Mechanistically Driven Approach to the Development of Atom-Efficient, Selective Catalytic Syntheses of Ureas, Carbamates, and Heterocycles. / Bruffaerts, Jeffrey; Von Wolff, Niklas; Diskin-Posner, Yael; Ben-David, Yehoshoa; Milstein, David.

In: Journal of the American Chemical Society, Vol. 141, No. 41, 16.10.2019, p. 16486-16493.

Research output: Contribution to journalArticle

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