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

doi:10.1021/jacs.9b08942

Back

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

Journal article

an open version is available

Peer reviewed

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 and David Milstein

Journal of the American Chemical Society, Vol.141(41), pp.16486-16493

16/Oct/2019

DOI: https://doi.org/10.1021/jacs.9b08942

Files and links (3)

pdf

dm_JACS_FormamidesasIsocyanate_AM20191.90 MBDownload View

AcceptedCC BY-NC-ND V4.0, Open Access

url

https://doi.org/10.1021/jacs.9b08942View

Published (Version of record)

url

https://figshare.com/articles/Formamides_as_Isocyanate_Surrogates_A_Mechanistically_Driven_Approach_to_the_Development_of_Atom-Efficient_Selective_Catalytic_Syntheses_of_Ureas_Carbamates_and_Heterocycles/9925118View

Preprint (Author's original)CC BY-NC V3.0, Open Access

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 a 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 or-ganometallic complexes, uniquely exhibiting the trapping of an isocyanate intermediate. DFT calculations further contributed to shed light on the remarkably orchestrated chain of catalytic events, involving metal-ligand cooperation.

Details

Title: Formamides as Isocyanate Surrogates; A Mechanistically Driven Approach to the Development of Atom-Efficient, Selective Catalytic Syntheses of Ureas, Carbamates, and Heterocycles
Creators: Jeffrey Bruffaerts - 972WIS_INST___97
Niklas Von Wolff - 972WIS_INST___97
Yael Diskin Posner - 972WIS_INST___100
Yehoshoa Ben-David - 972WIS_INST___97
David Milstein (Corresponding Author) - 972WIS_INST___97
Resource Type: Journal article
Publication Details: Journal of the American Chemical Society, Vol.141(41), pp.16486-16493; 16/Oct/2019
Number of pages: 8
Language: English
DOI: https://doi.org/10.1021/jacs.9b08942
Grants: New Directions in Sustainable Catalysis by Metal Complexes, 692775, European Research Council (Belgium, Brussels) - ERC
Grant note: This research was supported by the European Research Council (ERC AdG 692775). D.M. holds the Israel Matz Professorial Chair of Organic Chemistry. J.B. is thankful to the Feinberg graduate school for a postdoctoral fellowship. N.v.W. is supported by the Foreign Postdoctoral Fellowship Program of the Israel Academy of Sciences and Humanities.
Record Identifier: 992972320203596

Metrics

27 File views/ downloads

19 Record Views

See more details