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Ligand Control in Selective C–H Oxidative Functionalization Using Pd-PEPPSI-Type Complexes

Bolbat, Ekaterina LU and Wendt, Ola F. LU (2016) In European Journal of Organic Chemistry 2016(20). p.3395-3400
Abstract

To achieve high selectivity in directed C–H activation, an NHC ligand was introduced to a palladium catalyst. A range of Pd-PEPPSI complexes were applied in the direct acetoxylation of 2-phenylpyridine. The best catalyst was found to be the one based on a diisopropylphenyl-substituted NHC ligand, and this was successfully used for the functionalization of sp2as well as more challenging sp3bonds for a broad variety of substrates. The explored method showed a highly improved selectivity compared to previously reported results with up to 96 % yield for the monoacetoxylated product. Kinetic studies show that sterics of the catalyst is less important in dictating conversion and selectivity; despite an induction period,... (More)

To achieve high selectivity in directed C–H activation, an NHC ligand was introduced to a palladium catalyst. A range of Pd-PEPPSI complexes were applied in the direct acetoxylation of 2-phenylpyridine. The best catalyst was found to be the one based on a diisopropylphenyl-substituted NHC ligand, and this was successfully used for the functionalization of sp2as well as more challenging sp3bonds for a broad variety of substrates. The explored method showed a highly improved selectivity compared to previously reported results with up to 96 % yield for the monoacetoxylated product. Kinetic studies show that sterics of the catalyst is less important in dictating conversion and selectivity; despite an induction period, it was shown that the catalyst is molecular in nature.

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Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Acetoxylation, C-H activation, NHC ligands, Palladium
in
European Journal of Organic Chemistry
volume
2016
issue
20
pages
6 pages
publisher
John Wiley & Sons
external identifiers
  • scopus:84978715268
  • wos:000380138100019
ISSN
1434-193X
DOI
10.1002/ejoc.201600322
language
English
LU publication?
yes
id
36b69638-67e3-4557-8fc9-5c8751144e8d
date added to LUP
2017-01-16 15:28:44
date last changed
2017-09-18 11:31:59
@article{36b69638-67e3-4557-8fc9-5c8751144e8d,
  abstract     = {<p>To achieve high selectivity in directed C–H activation, an NHC ligand was introduced to a palladium catalyst. A range of Pd-PEPPSI complexes were applied in the direct acetoxylation of 2-phenylpyridine. The best catalyst was found to be the one based on a diisopropylphenyl-substituted NHC ligand, and this was successfully used for the functionalization of sp<sup>2</sup>as well as more challenging sp<sup>3</sup>bonds for a broad variety of substrates. The explored method showed a highly improved selectivity compared to previously reported results with up to 96 % yield for the monoacetoxylated product. Kinetic studies show that sterics of the catalyst is less important in dictating conversion and selectivity; despite an induction period, it was shown that the catalyst is molecular in nature.</p>},
  author       = {Bolbat, Ekaterina and Wendt, Ola F.},
  issn         = {1434-193X},
  keyword      = {Acetoxylation,C-H activation,NHC ligands,Palladium},
  language     = {eng},
  number       = {20},
  pages        = {3395--3400},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Organic Chemistry},
  title        = {Ligand Control in Selective C–H Oxidative Functionalization Using Pd-PEPPSI-Type Complexes},
  url          = {http://dx.doi.org/10.1002/ejoc.201600322},
  volume       = {2016},
  year         = {2016},
}