Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine

C. M. Che; K. W. Cheng; M. C W Chan; T. C. Lau; C. K. Mak

doi:10.1021/jo0010126

Author(s)

C. M. Che
K. W. Cheng
M. C W Chan
T. C. Lau
C. K. Mak

Detail(s)

Original language	English
Pages (from-to)	7996-8000
Journal / Publication	Journal of Organic Chemistry
Volume	65
Issue number	23
Publication status	Published - 17 Nov 2000

Link(s)

DOI	DOI https://doi.org/10.1021/jo0010126 Final Published version
	Check@CityULib
Link to Scopus	https://www.scopus.com/record/display.uri?eid=2-s2.0-0034680620&origin=recordpage
Permanent Link	https://scholars.cityu.edu.hk/en/publications/publication(951e21ed-5a10-4107-89e7-4f15f6a09d62).html

Abstract

The ruthenium(II) complex cis-[Ru(6,6'-Cl₂bpy)₂(OH₂)₂](CF₃SO₃)₂ (1) is a robust catalyst for C-H bond oxidations of hydrocarbons, including linear alkanes, using tert-butyl hydroperoxide (TBHP) as terminal oxidant. Alcohols can be oxidized by the '1 + TBHP' protocol to the corresponding aldehydes/ketones with high product yields at ambient temperature. Oxidation of 1 with Ce(IV) in aqueous solution affords cis-[Ru(VI)(6,6'-Cl₂bpy)₂O₂]²⁺, which is isolated as a green/yellow perchlorate salt (2). Complex 2 is a powerful stoichiometric oxidant for cycloalkane oxidations under mild conditions. Oxidation of cis-decalin is highly stereoretentive; cis-decalinol is obtained in high yield, and formation of trans-decalinol is not observed. Mechanistic studies showing a large primary kinetic isotope effect suggest a hydrogen-atom abstraction pathway. The relative reactivities of cycloalkanes toward oxidation by 2 have been examined through competitive experiments, and comparisons with Gif-type processes are presented.

Citation Format(s)

[ RIS ] [ BibTeX ]

Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine. / Che, C. M.; Cheng, K. W.; Chan, M. C W et al.

In: Journal of Organic Chemistry, Vol. 65, No. 23, 17.11.2000, p. 7996-8000.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62) › 21_Publication in refereed journal › peer-review

Che, CM, Cheng, KW, Chan, MCW, Lau, TC & Mak, CK 2000, 'Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine', Journal of Organic Chemistry, vol. 65, no. 23, pp. 7996-8000. https://doi.org/10.1021/jo0010126

Che, C. M., Cheng, K. W., Chan, M. C. W., Lau, T. C., & Mak, C. K. (2000). Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine. Journal of Organic Chemistry, 65(23), 7996-8000. https://doi.org/10.1021/jo0010126

Che CM, Cheng KW, Chan MCW, Lau TC, Mak CK. Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine. Journal of Organic Chemistry. 2000 Nov 17;65(23):7996-8000. doi: 10.1021/jo0010126

Che, C. M. ; Cheng, K. W. ; Chan, M. C W et al. / Stoichiometric and catalytic oxidations of alkanes and alcohols mediated by highly oxidizing ruthenium-oxo complexes bearing 6,6'-dichloro-2,2'-bipyridine. In: Journal of Organic Chemistry. 2000 ; Vol. 65, No. 23. pp. 7996-8000.