Novel Carboxymethylation of Styrene Derivatives by Mn3+-Mediated Electrooxidation

Shundo, R.; Nishiguchi, Ikuzo; Matsubara, Yoshiharu; Toyoshima, Manabu; Hirashima, Tsuneaki

doi:10.1246/cl.1991.185

Cited by 11 publications

(4 citation statements)

References 8 publications

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“…Mn(OAc) 3 ·2H 2 O is not particularly expensive on a laboratory scale, but its use on an industrial scale may be problematic. Several groups have demonstrated that Mn(III) can be used in catalytic quantities and regenerated electrochemically in situ . ,,,− In some cases, good yields of products are obtained with only 0.2 equiv (10%) of Mn(III) or Mn(II). In other cases the electrochemically mediated reactions proceed in substantially lower yield or give different products.…”

Section: Oxidants1 Mn(iii)mentioning

confidence: 99%

Manganese(III)-Based Oxidative Free-Radical Cyclizations

1996

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ContentsI. Introduction 339 A. Oxidative Free-Radical Cyclizations 339 B. Mn(OAc) 3 340 II. Initiation 341 A. Mechanistic Considerations 341 B. Substrates 342 C. Oxidants 342 1. Mn(III) 342 2. Ce(IV), Fe(III), V(V), etc. 343 D. Further Oxidation of the Product 344 III. Termination 345 A. Oxidation by Mn(III) 345 B. Oxidation by Cu(OAc) 2 345 C. Chlorination 346 D. Addition to Nitriles and Carbon Monoxide 346 E. Hydrogen Abstraction 347 IV. Monocyclization 347 A. Radicals Derived from Acids 348 B. Radicals Derived from β-Keto Esters and β-Diketones That Lead to Cycloalkanones 348 1. R-Unsubstituted β-Keto Esters 348 2. R-Substituted β-Keto Esters 349 3. Diketones 351 C. Radicals Derived from β-Keto Esters, β-Diketones, and Malonate Esters That Lead to Cycloalkanes 351 D. Radicals Derived from β-Keto Esters, β-Keto Amides, and Malonate Esters That Lead to Lactones and Lactams 351 E. Additions to Aromatic Rings 352 V. Tandem Cyclizations 353 A. Additions to a Double Bond and then an Arene 353 B. Additions to Two Double Bonds 354 VI. Triple and Higher Cyclizations 356 VII. Asymmetric Induction 356 VIII. Annulations 357 IX. Oxidation of Ketones 358 X. Oxidation of Enol Ethers and Enamines 359 XI. Fragmentation−Cyclizations 360 XII. Synthetic Applications 361 XIII. Acknowledgments 362 XIV. References and Notes 362Barry B. Snider is a graduate of the University of Michigan (B.S.) and Harvard University (Ph.D.). After postdoctoral training at Columbia University, he joined the faculty of Princeton University. Since 1981 he has been at Brandeis University, where he is now Professor of Chemistry. He has been an Alfred P. Sloan fellow, a Dreyfus Teacher Scholar and an ACS Cope Scholar. His research interests are in the area of synthetic methods development and natural product synthesis. Current interests include oxidative free-radical cyclizations, Lewis acid-induced and -catalyzed reactions, ene reactions, and the synthesis of guanidine-containing natural products.

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Section: Oxidants1 Mn(iii)mentioning

confidence: 99%

Manganese(III)-Based Oxidative Free-Radical Cyclizations

1996

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“…Addition products from 6b and diethyl 2-bromo-2-methylmalonate (21) [10,11] or dimethyl 2-bromo-3-ethylsuccinate 23 [13] were formed in 87 and 50%, respectively (scheme 5).…”

Section: Comentioning

confidence: 99%

Catalytic C,C-Bond Forming Additions to Unsaturated Fatty Compounds

Biermann

Metzger

2004

Topics in Catalysis

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A large number of novel fatty compounds have been synthesized by catalytic C,C-bond forming addition reactions to the C,Cdouble bond of unsaturated fatty compounds. Radical reactions such as the solvent-free addition of -halocarboxylic acid esters initiated by electron transfer, e.g., from copper to give fat-derived -lactones are described as well as Lewis acid-induced electrophilic addition reactions yielding new oleochemicals such as alkyl-substituted 4-chlorotetrahydropyrans, primary homoallylic alcohols, -, -unsaturated ketocarboxylic acids and Diels-Alder addition products. New catalysts as, e.g., ligandmodified rhodium catalysts for the hydroformylation and heterogeneous boron-modified rhenium catalysts for the olefin metathesis have been developed. The addition of C-nucleophiles such as dimethylmalonate and nitromethane is possible by palladium-(0)catalyzed additions to unsaturated fatty compounds after conversion of the electron-rich to an electron-poor double bond. More than fifty literature articles are reviewed.

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“…Using the Mn(OAc) 2 ±Cu(OAc) 2 mediator system, g-lactones have been obtained in acceptable yields from acetic acid and styrenes, 246,250 and alk-2-enyl-and cycloalk-2-enyl-substituted cyanoacetic esters were synthesised from ethyl cyanoacetate, alkenes and cycloalkenes. 246,247 In these reactions the carboxymethyl and (ethoxycarbonyl)cyanomethyl radicals together with their adducts with alkenes are formed as intermediates; the former species result from single-electron oxidation of acetic acid and ethyl cyanoacetate by electrogenerated Mn(OAc) 3 and the latter arise upon the addition of the primary radicals to alkenes.…”

Section: A Reactions Induced By Electrooxidation Of Manganese Compoundsmentioning

confidence: 99%

Electrochemical reactions of alkenes induced by anodic oxidation and their applications in organic synthesis

Ogibin¹,

Nikishin²

2001

Russ. Chem. Rev.

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Novel Carboxymethylation of Styrene Derivatives by Mn3+-Mediated Electrooxidation

Abstract: Anodic oxidation in a mixed solvent of acetic acid and acetic anhydride containing a variety of styrene derivatives, small amounts of Mn(OAc)2·4H2O and Cu(OAc)2·H2O brought about a facile carboxymethylation to give the corresponding γ-butyrolactones as the main products in good yields.

Cited by 11 publications

References 8 publications

Manganese(III)-Based Oxidative Free-Radical Cyclizations

Manganese(III)-Based Oxidative Free-Radical Cyclizations

Catalytic C,C-Bond Forming Additions to Unsaturated Fatty Compounds

Electrochemical reactions of alkenes induced by anodic oxidation and their applications in organic synthesis

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