Oxidation reactions of manganese(III) acetate. II. Formation of .gamma.-lactones from olefins and acetic acid

“…Related compounds including Mn(pic) 3 in DMF [manganese(III)picolinate] 13 and Mn(acac) 3 [manganese(III) acetoacetonate] 14 are capable of initiating similar reactions.…”

Section: Spotlightmentioning

confidence: 99%

“…1 Of particular importance is the use of Mn(OAc) 3 which acts as a one-electron oxidant. In 1968, it was shown to oxidise acetic acid leading to g-lactones in the presence of alkenes.…”

Section: Introductionmentioning

confidence: 99%

“…In 1968, it was shown to oxidise acetic acid leading to g-lactones in the presence of alkenes. 2,3 The mechanism of these reactions is not fully understood but is thought to proceed as shown in Scheme 1. Since then, a variety of alternative substrates to acetic acid, especially enolisable 1,3-dicarbonyls, have been successfully employed in related reactions, particularly cyclisations, to form 5-and 6membered rings.…”

Section: Introductionmentioning

confidence: 99%

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Manganese(III) acetate

Bar¹

2002

Synlett

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“…The first examples for oxidative free-radical cyclizations, including the use of Mn(OAc) 3 as the oxidant, was described by Heiba and Dessau [7] as well as Bush and Finkbeiner [8] in 1968 (Scheme 2). The first examples for oxidative free-radical cyclizations, including the use of Mn(OAc) 3 as the oxidant, was described by Heiba and Dessau [7] as well as Bush and Finkbeiner [8] in 1968 (Scheme 2).…”

Section: Manganese(iii) Acetate: Introduction and General Descriptionmentioning

confidence: 99%

Manganese(III) Acetate: A Versatile Reagent in Organic Chemistry

Demir¹,

Emrullahoğlu

2007

COS

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Free radical reactions have become increasingly important, as well as a very attractive tool, in organic synthesis within the last two decades, due to their powerful, selective, specific, and mild reaction abilities. Mn(OAc)3 mediated oxidative free radical reactions have been extensively developed in the last twenty years. Numerous regio-, chemo-, and stereoselective synthetic methods have been developed in both inter-and intramolecular reactions, and have detailed the progress of Mn(OAc)3 mediated oxidative free radical reactions since the end of the 19 th century. The new literature about the new synthetic methods on Mn(OAc)3 mediated carbon-carbon bond formation and carbon-oxygen bond formation reactions has not been extensively reviewed. The present paper summarizes the recent developments in oxidative free radical reactions mediated by Mn(OAc)3. Mn(OAc)3 mediated reactions of conjugated systems (e.g., alkenes, alkynes, 1,3-alkadienes, l,3-alkadiynes, 1-alken-3-ynes) with -dicarbonyl compounds, Mn(OAc)3 mediated alkylation, such as the oxidative addition of an aldehyde or ketone to alkenes, Mn(OAc)3 mediated free-radical cyclization of alkenes with active methylene compounds in the presence of oxygen to afford the cyclic peroxides; lactone synthesis by the Mn(OAc)3 mediated oxidative addition of carboxylic acids to alkenes, Mn(OAc)3 mediated cyclization of -(methylthio)acetamides, enamides, and -keto carboxamides to afford cyclic products.Mn(OAc)3 oxidative free-radical cyclizations of allylic -dicarbonyl compounds, for example, the cyclization of allylic -ketoesters to afford the corresponding -lactone. The reaction of alkenes with sodium azide in the presence of acetic acid was investigated to afford 1.2-diazides. The selective oxidation of enones led to '-acetoxy-enones by Mn(OAc)3 oxidation. In general, Mn(OAc)3 oxidations are characterized by higher '-regioselectivity and chemical yields, and milder reaction conditions, in turn tolerating many sensitive functional groups. The use of Mn(OAc)3 in combination with other carboxylic acids or manganese(II) carboxylates extends this methodology to the preparation of a variety of '-acyloxyenones that are otherwise inaccessible in a one-step procedure.

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Oxidation reactions of manganese(III) acetate. II. Formation of .gamma.-lactones from olefins and acetic acid

Cited by 174 publications

References 1 publication

The Oxidation of Organic Compounds by Active Manganese Dioxide

The Oxidation of Organic Compounds by Active Manganese Dioxide

Manganese(III) acetate

Manganese(III) Acetate: A Versatile Reagent in Organic Chemistry

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