Transfer hydrogenation and transfer hydrogenolysis. II. Catalytic activity of some soluble complexes in hydrogen transfer from alcohols to olefins and the mechanism of the reaction catalyzed by hydridotetrakis(triphenylphosphine)rhodium(I)

Imai, Hideaki; Nishiguchi, Takeshi; Fukuzumi, Kazuo

doi:10.1021/jo00925a004

Cited by 70 publications

(14 citation statements)

References 11 publications

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“…It is a square-planar, 16-electron complex, which catalyzes these reactions via different pathways depending on the hydrogen donor. The intermediate rhodium complexes tend to retain a fourcoordinated square-planar configuration, whereas the molecular hydrogen pathway proceeds through an octahedral state [35,[39][40][41][42] (Scheme 20.8).…”

Section: Transition Metal-catalyzed Reductionsmentioning

confidence: 99%

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Transfer Hydrogenation Including the Meerwein‐Ponndorf‐Verley Reduction

Klomp¹,

Hanefeld²,

Peters³

2006

The Handbook of Homogeneous Hydrogenation

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Section: Transition Metal-catalyzed Reductionsmentioning

confidence: 99%

“…The first step consists of the substitution of one of the ligands (L) of 18 by dioxane (39) in an oxidative addition (a) (Scheme 20.16). b-Elimination of 40 releases 2,3-dihydro-dioxine (41) and the 16-electron dihydrogen rhodium complex (42) (b).…”

Section: Transfer Hydrogenation Catalysts For Reduction Of C-c Doublementioning

confidence: 99%

Transfer Hydrogenation Including the Meerwein‐Ponndorf‐Verley Reduction

Klomp¹,

Hanefeld²,

Peters³

2006

The Handbook of Homogeneous Hydrogenation

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“…Based on the results described earlier and on a comparison with the mechanism of transfer hydrogenation of olefins (Imai et al, 1974;Nishiguchi and Fukuzumi, 1974;Nishiguchi et al, 1975), Scheme 2 was reasonably proposed for the catalytic cycle of hydrogen transfer reduction of aldehyde.…”

Section: Mechanistic Considerations and Rate Lawmentioning

confidence: 95%

Kinetic study of hydrogen transfer from benzyl alcohol to aliphatic aldehydes catalysed by heterogenised ruthenium(II) catalysts

Liu

Rempel

2010

Can J Chem Eng

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Aliphatic aldehydes were reduced to corresponding alcohols by transfer hydrogenation in the presence of Ru(II) complexes bound to swellable polymer matrices. Benzyl alcohol was used as hydrogen donor because of its strong hydrogen donor ability. The kinetics of the reaction has been measured between 100 and 140 • C. The results showed that reaction rate depended on the structure of aldehydes and concentrations of aldehyde. Also reaction rate depended on the concentration of hydrogen donor, and on the amount of catalyst. The reaction proceeded efficiently in halogenated hydrocarbon solvents. The metal leaching was different for different catalytic runs and it was most pronounced in the first catalytic run. The observed activation energy, E a = 18 ± 1 kcal/mol was obtained, suggested that process in predominantly chemically controlled reaction. A general reaction mechanism and rate equation have been proposed.

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“…chalcone, benzalacetone, acetophenone) also did not react with unsaturated alcohols under the conditions noted in Table 1. The combination of unsaturated alcohols as hydrogen donors and vinyl ketones as acceptors in the presence of Ru30(OOCCH3), or RuC1,-(P (C,M,),), is apparently the most reactive homogeneous intermolecular hydrogen transfer system so far reported (3)(4)(5)(6).…”

mentioning

confidence: 99%

“…Since the competitive intermolecular and intramolecular reactions proceed essentially at the same rate, they probably involve a similar rate determining step. Based on previous related studies (4,6,8) it would appear that this step involves the breaking of the C-H bond a to the hydroxyl in the donor. The hydride is then transferred directly, or via a metal hydride intermediate, to the bound unsaturated ketone or intramolecularly to the 3-position of the unsaturated alcohol.…”

mentioning

confidence: 99%