Cobalt(II) acetate promoted addition of acetoacetate to terminal olefins: A highly stereoselective synthesis of 5-alkyl-2-hydroxy 2 methyl-3-methoxycarbonyl tetrahydrofurans

Iqbal, Javed; Kumar, T. Kiran; Manogaran, S.

doi:10.1016/s0040-4039(01)80778-4

Cited by 18 publications

(3 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Citterio and co-workers have comprehensively explored the use of ferric perchlorate in acetonitrile for oxidative intermolecular additions of malonate esters to styrenes and oxidative cyclizations of unsaturated malonate esters and compared this reagent to Mn(OAc) 3 and ceric ammonium nitrate. ,,,,− Co(OAc) 2 and molecular oxygen in acetic acid have been used for the oxidative addition of β-diketones and β-keto esters to alkenes. The oxidant is probably Co(III), and the addition product is trapped with oxygen, leading to a dihydrofuran analogous to that formed in eq 4. − Baciocchi and co-workers have used ceric ammonium nitrate to oxidize malonate esters to radicals in alcohol solvents. , The utility of ceric ammonium nitrate for oxidative cyclization of malonate esters and β-keto esters to aromatic systems has been examined by Citterio and co-workers. − ,, …”

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

confidence: 99%

“…The oxidant is probably Co(III), and the addition product is trapped with oxygen, leading to a dihydrofuran analogous to that formed in eq 4. [140][141][142] Baciocchi and co-workers have used ceric ammonium nitrate to oxidize malonate esters to radicals in alcohol solvents. 119,143 The utility of ceric ammonium nitrate for oxidative cyclization of malonate esters and β-keto esters to aromatic systems has been examined by Citterio and coworkers.…”

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

confidence: 99%

See 1 more Smart Citation

Manganese(III)-Based Oxidative Free-Radical Cyclizations

1996

View full text Add to dashboard Cite

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.

show abstract

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

confidence: 99%

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

confidence: 99%

Manganese(III)-Based Oxidative Free-Radical Cyclizations

1996

View full text Add to dashboard Cite

show abstract

“…The yield of coupling product 27 in the reactions with the use of the Co 2+ /KMnO 4 and Co 2+ /Pb(OAc) 4 systems (runs 12–15 and 21) is substantially higher than that in the reactions with the oxidants KMnO 4 and Pb(OAc) 4 (runs 10, 11 and 20). The salts Mn(OAc) 3 78,79 and CAN80,81 and the Co 2+ /oxidant system82–84 have found use in the oxidative addition of 1,3‐dicarbonyl compounds to alkenes proceeding via the one‐electron oxidation of the former. Therefore, the experimental results and the literature data suggest that the oxidant in the reaction under study is involved both in the one‐electron oxidation of 1,3‐dicarbonyl compounds and the oxidation of NHPI to form PINO.…”

Section: Resultsmentioning

confidence: 99%

Why Is the Spontaneous Deprotonation of [Cu(uracil)₂]²⁺Complexes Accompanied by Enolization of the System?

et al. 2015

View full text Add to dashboard Cite

The reaction-force formalism is applied to carry out a detailed analysis of the mechanisms behind the enolization processes undergone by the complexes formed on interaction of uracil dimers with Cu(2+) ions after spontaneous deprotonation of the resulting complexes. These enolization processes apparently involve a single proton transfer (PT) from an NH group to a carbonyl group of the same uracil moiety, which should involve a rather high activation barrier that prevents the process occurring. However, the reaction-force, chemical-potential, and electronic-flux profiles unambiguously indicate that the actual mechanism involves three low-barrier elementary steps, and this explains why enolization of the [Cu(uracil-H)(uracil)](+) complexes is a highly facile, assisted PT process. All of the observed PT processes show a typical profile for both the chemical potential and the electronic flux associated with the bond-breaking and the bond-formation processes.

show abstract