Syntheses Involving Reactions of Peroxide Compounds With Salts of Transition Metals in Solution

Boguslavskaya, L. S.

doi:10.1070/rc1965v034n07abeh001498

Cited by 17 publications

(13 citation statements)

References 3 publications

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“…Hydrogen peroxide and its organic derivatives are catalytically decomposed by a variety of transition metal ions, and the free radicals thus generated participate in further oxidation and reduction reactions (36). An example is the novel use of Fenton's reagent [Fe"l and H2021 to add two azido moieties to alkenes by the following suggested mechanism (37):…”

Section: Synthesis With Free Radicals and Metal Complexesmentioning

confidence: 99%

Mechanisms of Organic Oxidation and Reduction by Metal Complexes

Kochi¹

1967

Science

137

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The mechanism of many organic oxidation and reduction reactions can be described in terms of the formation and reaction of free radicals with metal complexes. Redox (trace-metal) catalysis also involves the oxidation and reduction of radical intermediates with a metal species which oscillates between several oxidation states (4). The oxidation and reduction of free radicals with metal complexes follow two general mechanisms, electron transfer and ligand transfer. Direct analogy exists with wholly inorganic descriptions of outer-sphere and innersphere processes. In an electron transfer or outersphere mechanism the redox process is derived largely by transfer of an electron from reductant to oxidant, with only indirect contributions from the solvent and ligand. Carbonium ion intermediates and transition states are important considerations, and the scission of the beta-hydrogen bond is minor during oxidation of alkyl radicals to alkenes. In contrast, ligand transfer or inner-sphere mechanism demands maximum involvement of the ligand in the transition state. Free-radical character prevails; cationic contributions from the organic moiety are minimal. Oxidation and reduction are conjugate processes. In an electron transfer mechanism the oxidation of alkyl radicals to carbonium ions is conceptually represented by a microscopic reverse reaction in which a carbonium ion is reduced to an alkyl radical. A similar duality exists in the interconversion of carbanions and free radicals by metal complexes. The reversibility of the ligand transfer process is easier to observe. For example, the chlorine-transfer oxidation of alkyl radicals is represented by a microscopic reverse reduction of alkyl chlorides to alkyl radicals by cuprous chlorides. A ligand transfer counterpart of the reduction of radicals R*+Cu(II)Cl(n)<---->R-Cl+Cu(I)Cl(n-1) can also be described. Hopefully, these simple redox mechanisms will be utilized in rationalizing complex reactions and formulating new syntheses. The limited number of examples cited in this short review represent only an introduction to the vast area of chemical research to be tapped in the study of the mechanisms and the synthetic utility of oxidation-reduction reactions and catalysis.

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Section: Synthesis With Free Radicals and Metal Complexesmentioning

confidence: 99%

Mechanisms of Organic Oxidation and Reduction by Metal Complexes

Kochi¹

1967

Science

137

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“…2-(2-Quinolyl)cyclopentanol ( 4). -The cyclopentanone 2 (3 g) reduced with NaBH (0.5 g) in EtOH gave the cyclopentanol 4 from benzene: mp 97-98°; yield 2.9 g (96%); ir y™cl* 3550 cm-1; nmr (CC14) 1.6-2.6 (m, 5, cyclopentane + OH), 3.0-3.6 (m, 1, quinoline CH), 4.3-4.9 (m, 1, CHOH), 7.4 (d, 1, quinoline 3 , /3,4 = 9 Hz), and 7.6-8.3 (m, 5, quinoline H).…”

Section: Methodsmentioning

confidence: 99%

“…Caled for Ci9H2SNCh: C, 68.85; H, 7.55; N, 4.2. Found: C,68.3;H,7.4; N, 4.1. 31 was similarly prepared (88%): ir y*1™ 3405, 1725, and 753 cm-1; nmr (CCh) 1.44 [s,9,C(CH3)3] overlaying 1.4-2.0 (m, 2), 2.2-2.9 (m, 6), 3-3.9 (m, 5), 4.0-4.3 (m, 3), and 4,ArH).…”

Section: Methodsmentioning

confidence: 99%

“…6 Compound 2 failed to react with methylmagnesium iodide, as did also its hydrochloride, which is certainly in the quinoline form. Not unexpectedly, the compound 2 also failed to react under Knoevenagel conditions with (1) Part II: G. Jones and J, Wood, Tetrahedron, 21, 2961(1965.…”

mentioning

confidence: 99%

“…malononitrile, cyanoacetic esters, or cyanoacetamide, nor could an ethylene ketal be obtained. Reduction of the compound 2a with sodium borohydride gave 2- (2-quinolyl) cyclopentanol (4), which was dehydrated by distillation from potassium hydroxide to give 2-(2quinolyl) cyclopentene (5). We were unable to obtain Michael addition products from the cyclopentene 5 under a variety of conditions (listed in the Experimental Section) with malonic ester, cyanoacetic esters, or -butyl acetoacetate, and hence were forced to abandon this attempt to introduce the required twocarbon bridge for ring C.…”

mentioning

confidence: 99%

See 2 more Smart Citations

9-Aza steroids. III. Synthesis of some 2-cyclopentylquinolines as models for rings A, B, and D

Baty¹,

Jones²,

Moore³

1969

J. Org. Chem.

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Inorganic redox systems in graft polymerization onto cellulosic materials

Bains

1972

J. polym. sci., C Polym. symp.

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SYNOPSISA review is attempted of the inorganic redox systems in the context of free radical graft polymerization. Metal ion-H, 0, redox systems are considered as part of the spectrum of such inorganic and organic reagents used for the purpose. I t is%emphasized that the chemistry of these latter systems in particular is much like the radiation chemistry of aqueous solutions caused by high energy ionizing radiations. On the other hand, these systems involve low energy and therefore are less damaging to the substrate and relatively more specific. The reactivity of free radicals in these systems varies subtly with the system and the medium. It is observed that only ceric ion method and [Fe(II); Fe(III)] -H,O, system are most successful in grafting onto cellulosic materials. Attention is paid to the features which makes these systems so useful. Concrete results from ESR study are presented which underline the nonspecific nature of various free radical producing systems including radiations.

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Syntheses Involving Reactions of Peroxide Compounds With Salts of Transition Metals in Solution

Cited by 17 publications

References 3 publications

Mechanisms of Organic Oxidation and Reduction by Metal Complexes

Mechanisms of Organic Oxidation and Reduction by Metal Complexes

9-Aza steroids. III. Synthesis of some 2-cyclopentylquinolines as models for rings A, B, and D

Inorganic redox systems in graft polymerization onto cellulosic materials

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