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Pd-catalyzed carbonylative α-arylation of aryl bromides: scope and mechanistic studies.

Reaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative [alpha]-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba) sub(2)] (dba=dibenzylideneaceto... Full description

Journal Title: Chemistry (Weinheim an der Bergstrasse Germany), December 23, 2013, Vol.19(52), pp.17926-17938
Main Author: Nielsen, Dennis U
Other Authors: Lescot, Camille , Gøgsig, Thomas M , Lindhardt, Anders T , Skrydstrup, Troels
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1521-3765 ; DOI: 1521-3765 ; DOI: 10.1002/chem.201303384
Link: http://search.proquest.com/docview/1490785269/?pq-origsite=primo
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title: Pd-catalyzed carbonylative α-arylation of aryl bromides: scope and mechanistic studies.
format: Article
creator:
  • Nielsen, Dennis U
  • Lescot, Camille
  • Gøgsig, Thomas M
  • Lindhardt, Anders T
  • Skrydstrup, Troels
subjects:
  • Bromides–Chemistry
  • Catalysis–Chemistry
  • Molecular Structure–Chemistry
  • Oxidation-Reduction–Chemistry
  • Palladium–Chemistry
  • Stereoisomerism–Chemistry
  • Bromides
  • Palladium
  • 1,3-Diketones
  • Carbonylation
  • Palladium
  • Reaction Mechanisms
  • Synthetic Methods
ispartof: Chemistry (Weinheim an der Bergstrasse, Germany), December 23, 2013, Vol.19(52), pp.17926-17938
description: Reaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative [alpha]-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba) sub(2)] (dba=dibenzylideneacetone) as the palladium source and 1,3-bis(diphenylphosphino)propane (DPPP) as the bidentate ligand. These transformations were run in the two-chamber reactor, COware, applying only 1.5equivalents of carbon monoxide generated from the CO-releasing compound, 9-methylfluorene-9-carbonyl chloride (COgen). The methodology proved adaptable to a wide variety of aryl and heteroaryl bromides leading to a diverse range of aryl 1,3-diketones. A mechanistic investigation of this transformation relying on super(31)P and super(13)CNMR spectroscopy was undertaken to determine the possible catalytic pathway. Our results revealed that the combination of [Pd(dba) sub(2)] and DPPP was only reactive towards 4-bromoanisole in the presence of the sodium enolate of propiophenone suggesting that a [Pd(dppp)(enolate)] anion was initially generated before the oxidative-addition step. Subsequent CO insertion into an [Pd(Ar)(dppp)(enolate)] species provided the 1,3-diketone. These results indicate that a catalytic cycle, different from the classical carbonylation mechanism proposed by Heck, is operating. To investigate the effect of the dba ligand, the Pd super(0) precursor, [Pd( eta super(3)-1-PhC sub(3)H sub(4))( eta super(5)-C sub(5)H sub(5))], was examined. In the presence of DPPP, and in contrast to [Pd(dba) sub(2)], its oxidative addition with 4-bromoanisole occurred smoothly providing the [PdBr(Ar)(dppp)] complex. After treatment with CO, the acyl complex [Pd(CO)Br(Ar)(dppp)] was generated, however, its treatment with the sodium enolate led exclusively to the acylated enol in high yield. Nevertheless, the carbonylative [alpha]-arylation of 4-bromoanisole with either catalytic or stoichiometric [Pd( eta super(3)-1-PhC sub(3)H sub(4))( eta super(5)-C sub(5)H sub(5))] over a short reaction time, led to the 1,3-diketone product. Because none of the acylated enol was detected, this implied that a similar mechanistic pathway is operating as that observed for the same transformation with [Pd(dba) sub(2)] as the Pd source. CO-operation is the key! The first palladium-catalyzed carbonylative [alpha]-arylation of aryl bromides is described. A wide array of different aryl 1,3-diketones can be is
language: eng
source:
identifier: E-ISSN: 1521-3765 ; DOI: 1521-3765 ; DOI: 10.1002/chem.201303384
fulltext: fulltext
issn:
  • 15213765
  • 1521-3765
url: Link


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titlePd-catalyzed carbonylative α-arylation of aryl bromides: scope and mechanistic studies.
creatorNielsen, Dennis U ; Lescot, Camille ; Gøgsig, Thomas M ; Lindhardt, Anders T ; Skrydstrup, Troels
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ispartofChemistry (Weinheim an der Bergstrasse, Germany), December 23, 2013, Vol.19(52), pp.17926-17938
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subjectBromides–Chemistry ; Catalysis–Chemistry ; Molecular Structure–Chemistry ; Oxidation-Reduction–Chemistry ; Palladium–Chemistry ; Stereoisomerism–Chemistry ; Bromides ; Palladium ; 1,3-Diketones ; Carbonylation ; Palladium ; Reaction Mechanisms ; Synthetic Methods
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descriptionReaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative [alpha]-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba) sub(2)] (dba=dibenzylideneacetone) as the palladium source and 1,3-bis(diphenylphosphino)propane (DPPP) as the bidentate ligand. These transformations were run in the two-chamber reactor, COware, applying only 1.5equivalents of carbon monoxide generated from the CO-releasing compound, 9-methylfluorene-9-carbonyl chloride (COgen). The methodology proved adaptable to a wide variety of aryl and heteroaryl bromides leading to a diverse range of aryl 1,3-diketones. A mechanistic investigation of this transformation relying on super(31)P and super(13)CNMR spectroscopy was undertaken to determine the possible catalytic pathway. Our results revealed that the combination of [Pd(dba) sub(2)] and DPPP was only reactive towards 4-bromoanisole in the presence of the sodium enolate of propiophenone suggesting that a [Pd(dppp)(enolate)] anion was initially generated before the oxidative-addition step. Subsequent CO insertion into an [Pd(Ar)(dppp)(enolate)] species provided the 1,3-diketone. These results indicate that a catalytic cycle, different from the classical carbonylation mechanism proposed by Heck, is operating. To investigate the effect of the dba ligand, the Pd super(0) precursor, [Pd( eta super(3)-1-PhC sub(3)H sub(4))( eta super(5)-C sub(5)H sub(5))], was examined. In the presence of DPPP, and in contrast to [Pd(dba) sub(2)], its oxidative addition with 4-bromoanisole occurred smoothly providing the [PdBr(Ar)(dppp)] complex. After treatment with CO, the acyl complex [Pd(CO)Br(Ar)(dppp)] was generated, however, its treatment with the sodium enolate led exclusively to the acylated enol in high yield. Nevertheless, the carbonylative [alpha]-arylation of 4-bromoanisole with either catalytic or stoichiometric [Pd( eta super(3)-1-PhC sub(3)H sub(4))( eta super(5)-C sub(5)H sub(5))] over a short reaction time, led to the 1,3-diketone product. Because none of the acylated enol was detected, this implied that a similar mechanistic pathway is operating as that observed for the same transformation with [Pd(dba) sub(2)] as the Pd source. CO-operation is the key! The first palladium-catalyzed carbonylative [alpha]-arylation of aryl bromides is described. A wide array of different aryl 1,3-diketones can be isolated in good-to-excellent yields using only stoichiometric amounts of CO (see scheme). A mechanistic study is presented that suggests the need for enolate coordination prior to oxidative addition when [Pd(dba) sub(2)] is employed as the precatalyst.
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