New Metal Salt-Induced Homolytic Reactions. II. Modification of Free Radical Reactions by Copper Salts<sup>1</sup>

Kharasch, M. S.; Fono, Andrew

doi:10.1021/jo01087a007

Cited by 40 publications

(19 citation statements)

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“…The final product was generated through radical dimerization (Scheme 2). Thisr eactionm ode has also been revealed by Kharasch and Fono, [6] andM endenhall and Protasiewicz. [7] Subsequently,K agan reported ap hoto-Cannizzaro reaction of ortho-phthalaldehyde for the synthesis of g-lactonesi n 1966, [8] in which the key cyclization step proceeded through benzoyl radicala ddition to the aldehyde group.…”

Section: Acyl Radical Additionsupporting

confidence: 67%

“…M oreover, thermochemical calculations have been carriedo ut to clarify the key cyclizations tep [Eq. (6)], which predicts that the 5-endo cyclization of 2 to 3 is astrongly exothermic reaction (À26 kcal mol À1 ), whereas 4-exo-trig cyclization is strongly endothermic (+ 27 kcal mol À1 ), whicha ccounts for the favored pathway of 5-endo cyclization. Importantly,t he rate of this cyclization step has been measured to be extremely rapid (k 1 = 210 8 s À1 at 45 8C).…”

Section: Acyl Radical Additionmentioning

confidence: 99%

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Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

Liu

Lei

2015

Chemistry An Asian Journal

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Among various kinds of radical reactions, the addition of carbon-centered radicals to unsaturated bonds represents a powerful tool for the construction of different C-C and C-X (X = N, O, S, etc.) bonds, in which typically applied unsaturated bonds include alkenes, alkynes, imines, carbonyls, and even thiocarbonyls. When C=X bonds are utilized as the radical acceptors, reactions usually occur at the carbon position to generate a heteroatom radical, during which C-C coupling products are formed. This reaction mode has dominated this field for several decades. However, there is also another unconventional type of radical addition mode, in which carbon-centered radicals attack the heteroatom position of C=X bonds to generate carbon radicals, during which selective C-X bond formation is achieved. This reaction mode demonstrates an effective method for the construction of different C-X bonds, such as C-O, C-N, and C-S bonds. This Focus Review gives an overview of recent advances in this unconventional field.

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Section: Acyl Radical Additionsupporting

confidence: 67%

Section: Acyl Radical Additionmentioning

confidence: 99%

Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

Liu

Lei

2015

Chemistry An Asian Journal

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“…The rate of chain termination might either increase or decrease. In general, the decrease in the rate of propagation more than outweighs any decrease in the rate of termination (12,13) although the opposite effect has also been observed in the cobalt-catalyzed oxidation of cumene (14). * Since theory predicts a limiting rate equal to k32[RH]2/2k6 and since both k3 and ks will change if the radicals are complexed with the metal catalyst the measured limiting rate might be either larger or smaller?…”

Section: Iicelle Formation By the Catalystmentioning

confidence: 99%

The Metal-Catalyzed Autoxidation of Tetralin: I. Introduction. The Cobalt-Catalyzed Autoxidation in Acetic Acid

Kamiya¹,

Beaton²,

Lafortune³

et al. 1963

Can. J. Chem.

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The catalytic effect of transition metal salts on the rate of autoxidation of organic substances reaches a constant value at some critical catalyst concentration. Three possible explanations of this phenomena are critically examined. The cobalt acetate catalyzed autoxidation of tetralin in acetic acid has been reinvestigated and the limiting rate of oxidation at high cobalt concentrations has been shown to be due to the production of a steady-state concentration of hydroperoxide. The present results are in fair agreement with the experimental work of Woodward and Mesrobian (J. Am. Chem. Soc. 75, 6189 (1953)) and are in excellent agreement with theoretical predictions.

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“…The obtained results are shown in Table 3. The results presented in Table 3 indicate, that the best yields of DCP were obtained for systems consisting of NHPI and CuCl 2 ·2H 2 O, Co(OAc) 2 or Mn(acac) 2 (46%, 41% and 43% respectively). It can be concluded, that type of transition metal plays much more important role than type of anion in catalyst.…”

Section: The Influence Of Transition Metal Saltmentioning

confidence: 96%

<i>N</i>-Hydroxyphthalimide as a Catalyst of Cumene Oxidation with Hydroperoxide

Konopińska¹

2017

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Cumene oxidation with 1-methyl-1-phenylethyl hydroperoxide catalyzed by N-hydroxyphthalimide or its derivatives and transition metal salts has been studied. Effects of the type of metal compound (Co(II), Mn(II) or Cu(II) chloride, acetate or acetylacetonate), amounts of N-hydroxyphthalimide and metal salt as well as temperature were established. The highest yields of dicumyl peroxide (48-54%) were obtained, when reaction was performed at 60-70°C, in the presence of the NHPI/CuCl 2 catalytic system, in acetonitrile as a solvent. Similar yield of dicumyl peroxide (43%) was obtained in solvent-free medium.

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New Metal Salt-Induced Homolytic Reactions. II. Modification of Free Radical Reactions by Copper Salts¹

Cited by 40 publications

References 1 publication

Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

The Metal-Catalyzed Autoxidation of Tetralin: I. Introduction. The Cobalt-Catalyzed Autoxidation in Acetic Acid

<i>N</i>-Hydroxyphthalimide as a Catalyst of Cumene Oxidation with Hydroperoxide

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New Metal Salt-Induced Homolytic Reactions. II. Modification of Free Radical Reactions by Copper Salts1

Cited by 40 publications

References 1 publication

Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

Carbon‐Centered Radical Addition to C=X Bonds for C−X Bond Formation

The Metal-Catalyzed Autoxidation of Tetralin: I. Introduction. The Cobalt-Catalyzed Autoxidation in Acetic Acid

&lt;i&gt;N&lt;/i&gt;-Hydroxyphthalimide as a Catalyst of Cumene Oxidation with Hydroperoxide

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Product

Resources

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New Metal Salt-Induced Homolytic Reactions. II. Modification of Free Radical Reactions by Copper Salts¹

<i>N</i>-Hydroxyphthalimide as a Catalyst of Cumene Oxidation with Hydroperoxide