Transfer hydrogenation and transfer hydrogenolysis. 14. Cleavage of carbon-halogen bond by the hydrogen transfer from organic compounds catalyzed by noble metal salts

Imai, Hideaki; Nishiguchi, Takeshi; Tanaka, Mieko; Fukuzumi, Kazuo

doi:10.1021/jo00433a024

Cited by 38 publications

(21 citation statements)

References 5 publications

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“…Nitrogen-containing heterocyclic compounds, including 1,2,3,4-tetrahydroquinoline, piperidine, pyrrolidine and indoline, are also popular hydrogen donors for the reduction of aldehydes, alkenes, and alkynes [75,76]. With piperidine as hydrogen donor, the highly reactive 1-piperidene intermediate undergoes trimerization or, in the presence of amines, an addition reaction [77].…”

Section: Hydrogen Donorsmentioning

confidence: 99%

Transfer Hydrogenation Including the Meerwein‐Ponndorf‐Verley Reduction

Klomp¹,

Hanefeld²,

Peters³

2006

The Handbook of Homogeneous Hydrogenation

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Section: Hydrogen Donorsmentioning

confidence: 99%

Transfer Hydrogenation Including the Meerwein‐Ponndorf‐Verley Reduction

Klomp¹,

Hanefeld²,

Peters³

2006

The Handbook of Homogeneous Hydrogenation

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“…In the presence of H2 or various nucleophiles, chlorobenzene was catalytically carbonylated to b e n~a l d e h y d e , 6~~~~~~~~~~ benzoic alkyl b e n z o a t e~,~*~~*~~ and dialkylbenzamides73J4 in high yields. The carbonylation of 2-chlorobenzenesulfonamide smoothly gave saccharin in 91.4 5% yield.77 When the carbonylations were carried out in the presence of (tricyclohexy1phosphine)palladium complexes, higher temperatures and pressures (180 "C, [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] were employed than in the case of similar reactions catalyzed Since synthetic organic chemistry began, enhancement of the poor reactivity of nonactivated aryl halides toward nucleophiles has been one of the most challenging problems and desirable goals for chemists. Although this problem is still far from being completely solved, significant success has been achieved in promoting aromatic nucleophilic substitution by catalysis with various transition metal complexes.…”

Section: V Carbonylatlon Of Chloroarenesmentioning

confidence: 99%

“…Third, the influence of added halonickel(1) complex on the yield of the paramagnetic species and the reaction rate indicated that the formation of the Ni(1) and Ni(I1) complexes must have occurred subsequent to the rate-limiting step. The mechanism (eqs [18][19][20] involves slow, single electron transfer as the ratelimiting step, to give the tight ion pair, [L3Ni+ ArX-*] .…”

Section: I I Mechanistic Studies and Considerationsmentioning

confidence: 99%

“…[L4Nil a [L3Ni] + L (18) [L,Nil + ArHal-[L3Ni+ HalAr7 (19) Chlorobenzene (as well as some other reagents) oxidatively adds to the dimer, to furnish the a-aryl mononuclear compound [(dcpe)Pd(Ph)ClI, which is formed as though a [(dcpe)Pd] monomer were the reacting complex. It was, therefore, reasonable to propose an equilibrium between the monomer, [ (dcpe)-Pdl, and its well-characterized dimer.lM As both the cone angle and basicity of Cy3P are very close to those of i-Pr3P,166 one could anticipate a certain similarity in the same parameters between dcpe and dippp (although their chelating properties should be different).…”

Section: I I Mechanistic Studies and Considerationsmentioning

confidence: 99%

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Transformations of Chloroarenes, Catalyzed by Transition-Metal Complexes

Grushin¹,

Alper²

1994

Chem. Rev.

671

352

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“…A very intriguing reducing agent, N-benzyl-1,4-dihydronicotinamide (BNAH) as a NAD(P)H model has been applied by Yasui and associates [91]. Indoline had the highest hydrogendonating ability, and various bases (e.g., KOH) promoted the reaction [92]. Secondary cyclic amines proved to be useful reducing agents for the transfer hydrogenolysis of aryl halides with PdCl 2 as a catalyst in methanol at 140 8C.…”

Section: Hydrogen Donors Other Than Hydridesmentioning

confidence: 99%

Dehalogenation Reactions

and¹,

Simon²

2006

The Handbook of Homogeneous Hydrogenation

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Reductive dehalogenation -one of the earliest reactions described in the organic chemical literature -has achieved special significance since the 1980s when the harmful properties of numerous halogenated (chiefly chlorinated) hydrocarbons became clear. The identification of methods capable of neutralizing or, at least, diminishing these dangers, remains a major challenge for chemistry. It is reasonable to convert stocks of the prohibited chemicals (e.g., polychlorobiphenyls, PCBs; chlorofluorocarbons, CFCs) to valuable products as far as possible. At the same time, the halogen-containing wastes should be detoxified by degradation. During the past two decades, the mainly heterogeneous (but also homogeneous) catalytic dehalogenation provided a major share towards solving these problems. Within this period, substantial progress was also made in the application of these reactions in organic syntheses.Hydrodehalogenation -that is, hydrogenolysis of the carbon-halogen bondinvolves the displacement of a halogen bound to carbon by a hydrogen atom. This chapter is devoted to dehalogenations mediated by transition-metal complexes (Eq. (1)): ÀC j j ÀX reducing agent L n Mj 3 ÀC j j ÀH Y 1 where X = F, Cl, Br, I, and [L n M] = a transition metal complex. The use of a wide variety of reducing agents (H 2 , hydrides of metals and metalloids, organic reductants, etc.) under the most diverse reaction conditions (e.g., one-or two-phase systems) has been reported. Organic halides have also been reduced by electrochemical and photochemical methods in the presence of compounds of the type [L n M]. Reductive transformations of organic halides not relevant to Eq.(1) (e.g., coupling reactions) and dehalogenation of acyl halides will not be included here. 513The Handbook of Homogeneous Hydrogenation. Edited by J. G. de Vries and C. J. ElsevierThe reactivity of the carbon-halogen bond in Eq. (1) depends on several factors: · the nature of the halogen atom; · the environment of the halogen atom in the molecule; and · the reagents and conditions used in Eq. (1) [1].The order of reactivity of the C-X bond (generally: I > Br > Cl > F) is consistent with its strength. For instance, the experimentally found dissociation energies for phenyl halides (D Ph-X ) are 528, 402, 339, and 272 kJ mol -1 at 298 K for X = F, Cl, Br, and I, respectively [2]. Consequently, catalytic defluorination in the literature is comparatively rare. The different reactivity of the C-X bonds renders possible the selective dehalogenation of compounds containing two dissimilar halides, leaving intact the stronger C-X bond.

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Transfer hydrogenation and transfer hydrogenolysis. 14. Cleavage of carbon-halogen bond by the hydrogen transfer from organic compounds catalyzed by noble metal salts

Cited by 38 publications

References 5 publications

Transfer Hydrogenation Including the Meerwein‐Ponndorf‐Verley Reduction

Transfer Hydrogenation Including the Meerwein‐Ponndorf‐Verley Reduction

Transformations of Chloroarenes, Catalyzed by Transition-Metal Complexes

Dehalogenation Reactions

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