Insertion reactions of unsymmetrical ester-activated alkynes with o-benzylamine palladacycles: A regioselectivity study

Amy E. Kelly, Stuart A. Macgregor, Anthony C. Willis, John H. Nelson, Eric Wenger

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

The regioselectivities of the insertion reactions of RC=CCO2Et (R=Ph, CF3) into the aryl-palladium bond of several five-membered, ortho-palladated dimethylbenzylamine complexes, [PdCl(C6H4CH2NMe2-?C,N)] 2 (1), [PdCl(C6H4CH2NMe2-?C,N)(L)] [L=PEt3 (2), DMPP (3)], [Pd(C6H4CH2NMe2-?C,N) (NCMe)(L)]PF6 [L=MeCN (4), PEt3 (9), DMPP (5)], [Pd(OSO2CF3)(C6H4CH 2NMe2-?C,N)(DMPP)] (6), [Pd(C6H4CH2NMe2-?C,N) (solvent)]PF6 (7) and [Pd(C6H4CH2NMe2-?C,N) (DMPP)(solvent)]PF6 (8), have been compared with the help of multinuclear NMR spectroscopy. In general, the carboxylate group in the resulting seven-membered palladacycles is preferentially located next to the phenyl group of the benzylamine moiety, but this substitution pattern can be reversed by use of complexes containing electron-deficient and/or coordinatively-unsaturated palladium centres. A mechanism, based both on the experimental results described in this paper and on DFT computations, is proposed. © 2003 Elsevier Science B.V. All rights reserved.

Original languageEnglish
Pages (from-to)79-97
Number of pages19
JournalInorganica Chimica Acta
Volume352
DOIs
Publication statusPublished - 6 Aug 2003

Keywords

  • Alkyne insertion
  • DFT calculation
  • Dimethylbenzylamine
  • NMR spectroscopy
  • Palladacycles
  • Regiochemistry

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