Aerobic dehydrogenation of cyclohexanone to cyclohexenone catalyzed by Pd(DMSO)2(TFA)2: Evidence for ligand-controlled chemoselectivity

Tianning Diao, Doris Pun, Shannon S. Stahl

Research output: Contribution to journalArticle

Abstract

The dehydrogenation of cyclohexanones affords cyclohexenones or phenols via removal of 1 or 2 equiv of H2, respectively. We recently reported several PdII catalyst systems that effect aerobic dehydrogenation of cyclohexanones with different product selectivities. Pd(DMSO) 2(TFA)2 is unique in its high chemoselectivity for the conversion of cyclohexanones to cyclohexenones, without promoting subsequent dehydrogenation of cyclohexenones to phenols. Kinetic and mechanistic studies of these reactions reveal the key role of the dimethylsulfoxide (DMSO) ligand in controlling this chemoselectivity. DMSO has minimal kinetic influence on the rate of Pd(TFA)2-catalyzed dehydrogenation of cyclohexanone to cyclohexenone, while it strongly inhibits the second dehydrogenation step, conversion of cyclohexenone to phenol. These contrasting kinetic effects of DMSO provide the basis for chemoselective formation of cyclohexenones.

Original languageEnglish (US)
Pages (from-to)8205-8212
Number of pages8
JournalJournal of the American Chemical Society
Volume135
Issue number22
DOIs
StatePublished - Jun 5 2013

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Cyclohexanones
Dehydrogenation
Dimethyl Sulfoxide
Ligands
Phenols
Kinetics
Phenol
cyclohexanone
Catalysts

ASJC Scopus subject areas

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

Cite this

Aerobic dehydrogenation of cyclohexanone to cyclohexenone catalyzed by Pd(DMSO)2(TFA)2 : Evidence for ligand-controlled chemoselectivity. / Diao, Tianning; Pun, Doris; Stahl, Shannon S.

In: Journal of the American Chemical Society, Vol. 135, No. 22, 05.06.2013, p. 8205-8212.

Research output: Contribution to journalArticle

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