Palladium/Rhodium Cooperative Catalysis for the Production of Aryl Aldehydes and Their Deuterated Analogues Using the Water–Gas Shift Reaction

Malek Y.S. Ibrahim, Scott E Denmark

Research output: Contribution to journalArticle

Abstract

A novel Pd/Rh dual-metallic cooperative catalytic process has been developed to effect the reductive carbonylation of aryl halides in moderate to good yield. In this reaction, water is the hydride source, and CO serves both as the carbonyl source and the terminal reductant through the water–gas shift reaction. The catalytic generation of the Rh hydride allows for the selective formation of highly hindered aryl aldehydes that are inaccessible through previously reported reductive carbonylation protocols. Moreover, aldehydes with deuterated formyl groups can be efficiently and selectively synthesized using D2O as a cost-effective deuterium source without the need for presynthesizing the aldehyde.

Original languageEnglish (US)
Pages (from-to)10362-10367
Number of pages6
JournalAngewandte Chemie - International Edition
Volume57
Issue number32
DOIs
StatePublished - Aug 6 2018

Fingerprint

Rhodium
Palladium
Aldehydes
Catalysis
Carbonylation
Hydrides
Deuterium
Reducing Agents
Carbon Monoxide
Water
Costs

Keywords

  • aldehydes
  • aryl halides
  • carbonylation
  • cooperative catalysis
  • water–gas shift reaction

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

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abstract = "A novel Pd/Rh dual-metallic cooperative catalytic process has been developed to effect the reductive carbonylation of aryl halides in moderate to good yield. In this reaction, water is the hydride source, and CO serves both as the carbonyl source and the terminal reductant through the water–gas shift reaction. The catalytic generation of the Rh hydride allows for the selective formation of highly hindered aryl aldehydes that are inaccessible through previously reported reductive carbonylation protocols. Moreover, aldehydes with deuterated formyl groups can be efficiently and selectively synthesized using D2O as a cost-effective deuterium source without the need for presynthesizing the aldehyde.",
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AB - A novel Pd/Rh dual-metallic cooperative catalytic process has been developed to effect the reductive carbonylation of aryl halides in moderate to good yield. In this reaction, water is the hydride source, and CO serves both as the carbonyl source and the terminal reductant through the water–gas shift reaction. The catalytic generation of the Rh hydride allows for the selective formation of highly hindered aryl aldehydes that are inaccessible through previously reported reductive carbonylation protocols. Moreover, aldehydes with deuterated formyl groups can be efficiently and selectively synthesized using D2O as a cost-effective deuterium source without the need for presynthesizing the aldehyde.

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KW - cooperative catalysis

KW - water–gas shift reaction

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