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Regioselectivity in C-H activation: reagent control in cyclometallation of 2-(1-naphthyl)-pyridine.

Kondrashov, Mikhail LU ; Provost, David and Wendt, Ola LU (2016) In Dalton Transactions 45(2). p.525-531
Abstract
2-(1-Naphthyl)-pyridine () possesses sp(2) C-H bonds in both the γ- and δ-positions and is therefore a suitable substrate for studying the cyclometallation selectivity with different reagents and conditions. Such selectivity studies are reported. Based on deuterium-exchange experiments it is concluded that cycloruthenation with RuCl2(p-cymene) dimer is reversible with kinetic and thermodynamic preference for γ-substitution. Electrophilic cycloborylation, on the other hand, shows unusual δ-substitution. The previously published cyclopalladation and cycloauration of the substrate was studied in detail and was shown to be irreversible; they proceed under kinetic control and give γ- and δ-substitution for palladium and gold, respectively.
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
volume
45
issue
2
pages
525 - 531
publisher
Royal Society of Chemistry
external identifiers
  • pmid:26597047
  • wos:000367312900018
  • scopus:84952793987
ISSN
1477-9234
DOI
10.1039/c5dt04068j
language
English
LU publication?
yes
id
48a5bb68-38f6-4704-a7b0-c583bed8404f (old id 8234821)
date added to LUP
2015-12-16 17:31:37
date last changed
2017-08-13 03:15:51
@article{48a5bb68-38f6-4704-a7b0-c583bed8404f,
  abstract     = {2-(1-Naphthyl)-pyridine () possesses sp(2) C-H bonds in both the γ- and δ-positions and is therefore a suitable substrate for studying the cyclometallation selectivity with different reagents and conditions. Such selectivity studies are reported. Based on deuterium-exchange experiments it is concluded that cycloruthenation with RuCl2(p-cymene) dimer is reversible with kinetic and thermodynamic preference for γ-substitution. Electrophilic cycloborylation, on the other hand, shows unusual δ-substitution. The previously published cyclopalladation and cycloauration of the substrate was studied in detail and was shown to be irreversible; they proceed under kinetic control and give γ- and δ-substitution for palladium and gold, respectively.},
  author       = {Kondrashov, Mikhail and Provost, David and Wendt, Ola},
  issn         = {1477-9234},
  language     = {eng},
  number       = {2},
  pages        = {525--531},
  publisher    = {Royal Society of Chemistry},
  series       = {Dalton Transactions},
  title        = {Regioselectivity in C-H activation: reagent control in cyclometallation of 2-(1-naphthyl)-pyridine.},
  url          = {http://dx.doi.org/10.1039/c5dt04068j},
  volume       = {45},
  year         = {2016},
}