Synthesis of Active Hexafluoroisopropyl Benzoates through a Hydrogen-Bond-Enabled Palladium(II)-Catalyzed C−H Alkoxycarbonylation Reaction

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19 Citations (Scopus)

Abstract

A PdII-catalyzed ortho C−H alkoxycarbonylation reaction of aryl silanes toward active hexafluoroisopropyl (HFIP) benzoate esters has been developed. This efficient reaction features high selectivity and good functional-group tolerance. Notably, given the general nature of the silyl-tethered directing group, this method delivers products bearing two independently modifiable sites. NMR studies reveal the presence of hydrogen bonding between HFIP and a pyrimidine nitrogen atom of the directing group, and it is thought to be crucial for the success of this alkoxycarbonylation reaction.

Original languageEnglish (US)
Pages (from-to)3191-3195
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number12
DOIs
StatePublished - Jan 1 2017
Externally publishedYes

Fingerprint

Bearings (structural)
Silanes
Benzoates
Palladium
Functional groups
Esters
Hydrogen bonds
Nitrogen
Nuclear magnetic resonance
Atoms
pyrimidine

Keywords

  • C−H activation
  • heterocycles
  • hydrogen bonds
  • palladium
  • silane

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

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title = "Synthesis of Active Hexafluoroisopropyl Benzoates through a Hydrogen-Bond-Enabled Palladium(II)-Catalyzed C−H Alkoxycarbonylation Reaction",
abstract = "A PdII-catalyzed ortho C−H alkoxycarbonylation reaction of aryl silanes toward active hexafluoroisopropyl (HFIP) benzoate esters has been developed. This efficient reaction features high selectivity and good functional-group tolerance. Notably, given the general nature of the silyl-tethered directing group, this method delivers products bearing two independently modifiable sites. NMR studies reveal the presence of hydrogen bonding between HFIP and a pyrimidine nitrogen atom of the directing group, and it is thought to be crucial for the success of this alkoxycarbonylation reaction.",
keywords = "C−H activation, heterocycles, hydrogen bonds, palladium, silane",
author = "Yang Wang and Vladimir Gevorgyan",
year = "2017",
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doi = "10.1002/anie.201611757",
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T1 - Synthesis of Active Hexafluoroisopropyl Benzoates through a Hydrogen-Bond-Enabled Palladium(II)-Catalyzed C−H Alkoxycarbonylation Reaction

AU - Wang, Yang

AU - Gevorgyan, Vladimir

PY - 2017/1/1

Y1 - 2017/1/1

N2 - A PdII-catalyzed ortho C−H alkoxycarbonylation reaction of aryl silanes toward active hexafluoroisopropyl (HFIP) benzoate esters has been developed. This efficient reaction features high selectivity and good functional-group tolerance. Notably, given the general nature of the silyl-tethered directing group, this method delivers products bearing two independently modifiable sites. NMR studies reveal the presence of hydrogen bonding between HFIP and a pyrimidine nitrogen atom of the directing group, and it is thought to be crucial for the success of this alkoxycarbonylation reaction.

AB - A PdII-catalyzed ortho C−H alkoxycarbonylation reaction of aryl silanes toward active hexafluoroisopropyl (HFIP) benzoate esters has been developed. This efficient reaction features high selectivity and good functional-group tolerance. Notably, given the general nature of the silyl-tethered directing group, this method delivers products bearing two independently modifiable sites. NMR studies reveal the presence of hydrogen bonding between HFIP and a pyrimidine nitrogen atom of the directing group, and it is thought to be crucial for the success of this alkoxycarbonylation reaction.

KW - C−H activation

KW - heterocycles

KW - hydrogen bonds

KW - palladium

KW - silane

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JO - Angewandte Chemie - International Edition

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