Intramolecular radical coupling of a phenolic enolate: Oxidative fragmentation of the spirodiketone intermediate

Leboff, A.; Carbonnelle, Annie-Claude; Alazard, J.-P.; Thal, C.; Kende, Andrew S.

doi:10.1016/s0040-4039(00)95567-9

Cited by 17 publications

(3 citation statements)

References 4 publications

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“…Hirao et al have used VO(OEt)Cl 2 to generate radicals from diketene in ethanol . Kende has shown that alkaline potassium ferricyanide induces oxidative cyclization of phenols with a side chain bearing a nitro group or a readily enolizable carbonyl group (eqs 9 and 10). − These reactions probably proceed by oxidation to the radical, cyclization to the radical anion, and further oxidation as shown in eq 10. Analogous reactions have also been carried out with Mn(OAc) 3 in a model study for fredericamycin A…”

Section: Ce(iv) Fe(iii) V(v) Etcmentioning

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: Ce(iv) Fe(iii) V(v) Etcmentioning

confidence: 99%

Manganese(III)-Based Oxidative Free-Radical Cyclizations

1996

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“…Our literature survey revealed that several alkyl groups (methyl, [7][8][9][10] ethyl, [11] t-butyl [12,13] ) have been used to protect the phenolic compounds; however, they need drastic conditions for protection as well as deprotection, which also affect other functional groups. Newer protecting groups such as methoxymethylchloride (MOMCl) [14][15][16][17][18] methoxyethoxymethylchloride (MEMCl), [19] 2-(trimethylsilyl) ethoxymethylchoride (SEMCl), [20,21] and tetrahydrophyranoether (THP ethers) [22,23] have been developed that needs milder conditions. The prenyl group has also been used for protection of alcohols and phenols; [24][25][26][27][28][29][30][31][32][33][34] however, the reported reagents in deprotection of the prenyl group lack selectivity in multifunctional compounds.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient and Selective Deprotection Method for Prenyl, Geranyl, and Phytyl Ethers and Esters Using Borontrifluoride–Etherate

Narender

Venkateswarlu

Madhur

et al. 2012

Synthetic Communications

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“…Concentrating the reaction of potassium ferricyanide with 3 yielded a cyclization product resorufamine (Scheme ). ,,− …”

Section: Results and Discussionmentioning

confidence: 99%

Mechanistic Insights into Oxidative Oligomerization of p-Phenylenediamine and Resorcinol

2016

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An efficient synthesis of a green dye from oxidative coupling of p-phenylenediamine (PPD) and resorcinol (in a 2:1 ratio) has been developed. Reactivity studies of this dye molecule with a variety of reagents (PPD, resorcinol, the oxidized form of the green dye itself, and a dinuclear indo dye) demonstrate that it cannot be the key reactive intermediate in reported oxidative oligomerization of PPD and resorcinol. However, the trinuclear species does form large aggregates. At least one viable pathway of oligomerization has been demonstrated with the dinuclear indo dye.

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Intramolecular radical coupling of a phenolic enolate: Oxidative fragmentation of the spirodiketone intermediate

Cited by 17 publications

References 4 publications

Manganese(III)-Based Oxidative Free-Radical Cyclizations

Manganese(III)-Based Oxidative Free-Radical Cyclizations

Highly Efficient and Selective Deprotection Method for Prenyl, Geranyl, and Phytyl Ethers and Esters Using Borontrifluoride–Etherate

Mechanistic Insights into Oxidative Oligomerization of p-Phenylenediamine and Resorcinol

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