Catalytic cross-coupling reaction of esters with organoboron compounds and decarbonylative reduction of esters with HCOONH4

A new route to acyl transition metal complexes through the cleavage of acyl-oxygen bonds in esters

Hiroto Tatamidani, Kazuhiko Yokota, Fumitoshi Kakiuchi, Naoto Chatani

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77 Citations (Scopus)

Abstract

The Ru3(CO)12-catalyed cross-coupling reaction of esters with organoboron compounds leading to ketones is described. A wide variety of functional groups can be tolerated under the reaction conditions. Aromatic boronates function as a coupling partner to give aryl ketones. Acyl-alkyl coupling to dialkyl ketones is also achieved by the use of 9-alkyl-9-BBN in place of boronates. The Ru3(CO)12- catalyzed decarbonylative reduction of esters with ammonium formate (HCOONH 4) leading to hydrocarbons is also described. No expected aldehydes are produced, and controlled experiments indicate that aldehydes are not intermediate for the transformation. A hydrosilane can also be used as a reducing reagent in place of HCOONH4. A wide variety of functional groups are compatible for both reactions. The key step for both catalytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.

Original languageEnglish
Pages (from-to)5615-5621
Number of pages7
JournalJournal of Organic Chemistry
Volume69
Issue number17
DOIs
Publication statusPublished - 2004 Aug 20
Externally publishedYes

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Coordination Complexes
Ketones
Transition metals
Esters
formic acid
Carbon Monoxide
Oxygen
Aldehydes
Functional groups
Hydrocarbons
Carbon
Experiments

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Catalytic cross-coupling reaction of esters with organoboron compounds and decarbonylative reduction of esters with HCOONH4: A new route to acyl transition metal complexes through the cleavage of acyl-oxygen bonds in esters",
abstract = "The Ru3(CO)12-catalyed cross-coupling reaction of esters with organoboron compounds leading to ketones is described. A wide variety of functional groups can be tolerated under the reaction conditions. Aromatic boronates function as a coupling partner to give aryl ketones. Acyl-alkyl coupling to dialkyl ketones is also achieved by the use of 9-alkyl-9-BBN in place of boronates. The Ru3(CO)12- catalyzed decarbonylative reduction of esters with ammonium formate (HCOONH 4) leading to hydrocarbons is also described. No expected aldehydes are produced, and controlled experiments indicate that aldehydes are not intermediate for the transformation. A hydrosilane can also be used as a reducing reagent in place of HCOONH4. A wide variety of functional groups are compatible for both reactions. The key step for both catalytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.",
author = "Hiroto Tatamidani and Kazuhiko Yokota and Fumitoshi Kakiuchi and Naoto Chatani",
year = "2004",
month = "8",
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TY - JOUR

T1 - Catalytic cross-coupling reaction of esters with organoboron compounds and decarbonylative reduction of esters with HCOONH4

T2 - A new route to acyl transition metal complexes through the cleavage of acyl-oxygen bonds in esters

AU - Tatamidani, Hiroto

AU - Yokota, Kazuhiko

AU - Kakiuchi, Fumitoshi

AU - Chatani, Naoto

PY - 2004/8/20

Y1 - 2004/8/20

N2 - The Ru3(CO)12-catalyed cross-coupling reaction of esters with organoboron compounds leading to ketones is described. A wide variety of functional groups can be tolerated under the reaction conditions. Aromatic boronates function as a coupling partner to give aryl ketones. Acyl-alkyl coupling to dialkyl ketones is also achieved by the use of 9-alkyl-9-BBN in place of boronates. The Ru3(CO)12- catalyzed decarbonylative reduction of esters with ammonium formate (HCOONH 4) leading to hydrocarbons is also described. No expected aldehydes are produced, and controlled experiments indicate that aldehydes are not intermediate for the transformation. A hydrosilane can also be used as a reducing reagent in place of HCOONH4. A wide variety of functional groups are compatible for both reactions. The key step for both catalytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.

AB - The Ru3(CO)12-catalyed cross-coupling reaction of esters with organoboron compounds leading to ketones is described. A wide variety of functional groups can be tolerated under the reaction conditions. Aromatic boronates function as a coupling partner to give aryl ketones. Acyl-alkyl coupling to dialkyl ketones is also achieved by the use of 9-alkyl-9-BBN in place of boronates. The Ru3(CO)12- catalyzed decarbonylative reduction of esters with ammonium formate (HCOONH 4) leading to hydrocarbons is also described. No expected aldehydes are produced, and controlled experiments indicate that aldehydes are not intermediate for the transformation. A hydrosilane can also be used as a reducing reagent in place of HCOONH4. A wide variety of functional groups are compatible for both reactions. The key step for both catalytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.

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