Selective sp3 C-H activation of ketones at the β position by Ir(I). Origin of regioselectivity and water effect

Moran Feller, Amir Karton, Gregory Leitus, Jan M.L. Martin, David Milstein

Research output: Contribution to journalArticlepeer-review

62 Citations (Scopus)

Abstract

The reaction of the cationic (PNP)Ir(I)(cyclooctene) complex (1) (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) with 2-butanone or 3-pentanone results in the selective, quantitative activation of a β C-H bond, yielding O,C-chelated complexes. Calculations show that the selectivity is both kinetically (because of steric reasons in the rate determingin step (RDS)) and thermodynamically controlled, the latter as a result of carbonyl oxygen coordination in the product. The RDS is formation of the η2-C,H intermediates from the complexed ketone intermediates. Water has a strong influence on the regioselectivity, and in its presence, reaction of 1 with 2-butanone gives also the α terminal C-H activation product. Computational studies suggest that water can stabilize the terminal α C-H activation product by hydrogen bonding, forming a six-membered ring with the ketone, as experimentally observed in the X-ray structure of the acetonyl hydride aqua complex.

Original languageEnglish
Pages (from-to)12400-12401
Number of pages2
JournalJournal of the American Chemical Society
Volume128
Issue number38
DOIs
Publication statusPublished - Sep 27 2006

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Selective sp<sup>3</sup> C-H activation of ketones at the β position by Ir(I). Origin of regioselectivity and water effect'. Together they form a unique fingerprint.

Cite this