The Baeyer-Villiger Oxidation of Bicyclic Ketones

Meinwald, Jerrold; Frauenglass, E.

doi:10.1021/ja01504a052

Cited by 78 publications

(19 citation statements)

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“…Without buffer he observed a Meinwald and Frauenglass supported the boat/chair model and were in contradiction to the modified mechanism of mixture of lactones [76] and in presence of the strong sulfuric acid he obtained only the regioisomer 12c in 30% yield (en-Sauers in strongly acidic solution. [79] The product distribution was similar in buffered conditions (entry 1, Table 3) try 5, Table 3). [76] These were the first results of different product selectivit-or in strongly acidic medium (entry 2, Table 3).…”

Section: Migrating Groupmentioning

confidence: 95%

100 Years of Baeyer–Villiger Oxidations

Renz

Meunier²

1999

Eur. J. Org. Chem.

554

307

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In the present review, we report the discovery of the formation of esters and lactones by oxidation of ketones with a peroxide derivative, namely the Baeyer–Villiger reaction. This reaction was first reported by Adolf von Baeyer and Victor Villiger a century ago in 1899, just one year after the oxidant they used (KHSO5) has been described. Furthermore, Baeyer and Villiger established the composition of this new inorganic peroxide and showed that its instability was the reason of a controversy between several European chemists between 1878 and 1893. For the first 50 years the mechanism of the Baeyer–Villiger reaction was a matter of debate. A side product, 1,2,4,5‐tetraoxocyclohexane, was ruled out as an intermediate in the ester formation by Dilthey. Criegee postulated a nucleophilic attack of the oxidant on the carbonyl group. This mechanism was confirmed by von E. Doering by a labeling experiment with [18O]benzophenone. The rearrangement step occurs with retention of the stereochemistry at the migrating center. The competitive migration and the rate‐determining step are also discussed in this review.

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Section: Migrating Groupmentioning

confidence: 95%

100 Years of Baeyer–Villiger Oxidations

Renz

Meunier²

1999

Eur. J. Org. Chem.

554

307

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“…All compounds described, including the final spiroacetals 22-28, were obtained pure. Commercially available 6 -valerolactone (1) was purchased from Aldrich Chemicul Cumpuny Inc. and used without any further purification, 5-methyl-6-valerolactone (2) was obtained by catalytic hydrogenation (see below) of 3,6-dihydro-6-methyl-2H-pyran-2-one [21], and trans-perhydro-lH-2-benzopyran-3-one (3) was prepared by a well known procedure: Bueyer-Villiger oxidation [22] of trans-hydrindanone [23]. 1R Spectra: Perkin-Elmer-681 spectrophotometer.…”

Section: Experimental Partmentioning

confidence: 99%

Cyclization of Hydroxyenol Ethers into Spiroacetals. Evidence for the position of the transition state and its implication on the stereoelectronic effects in acetal formation

Pothier¹,

Goldstein²,

Deslongchamps³

1992

Helvetica Chimica Acta

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Acid-catalyzed cyclizations under thermodynamically and kinetically controlled conditions of the hydroxyenol ethers 18-21 are reported. Thermodynamically controllcd cyclizations of 18, 19, and 21 produced only the more stable corresponding spiroacetals 22 and 27. Thermodynamically controlled cyclization of compound 20 produced a 1:l mixture of non-epimerisable spiroacetals 24 and 26. On the other hand, kinetically controlled cyclizations of the same four hydroxyenol ethers produced, along with the more stable spiroacetals mentioned above, the less stable spiroacetals 23,25, and 28. These results show that the kinetically controlled cyclizalion takes place via an early transition state which produces a mixture of the less stable and the more stable isomers. These results are explained by an early transition state taking into account the principle of stereoelectronic control while following the antiperiplanar lone-pair hypothesis (Burgi-Dunirz angle of attack of a nucleophile on a n systcm).Introduction. -We previously reported [ 11 a study which revealed that the unsubstituted 1,7-dioxaspiro[5.5]undecane exists exclusively in conformation A, (Scheme I ), even at room temperature. This experimental observation was explained by the fact that conformation A, is stereoelectronically and sterically more stable than conformations A, and A, which were estimated to be less stable by a value of 2.4 and 4.8 kcal/mol, respectively'). This result was further confirmed experimentally by comparing the behavior of l-oxaspiro[5.5]undecane which was shown to exist as an equilibrium mixture of two conformers [2].

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“…Lactone 5 was obtained by Baeyer-Villiger oxidation of commercially available 5-methylcyclopentanone (28). transOctahydrocoumarin (6) was prepared according to the procedure of Graham and co-workers (29).…”

Section: Preparation Of Lactonesmentioning

confidence: 99%

Structural studies on 6-ethoxytetrahydropyrylium cations; stereoelectronic control in the reactions of lactonium salts

Childs¹,

Kostyk²,

Lock³

et al. 1991

Can. J. Chem.

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. Can. J. Chem. 69,2024Chem. 69, (1991.The structures of 6-ethoxy-2,3,4,5-tetrahydropyrylium, 1, 6-eth0xy-2-methyl-2,3,4,5-tetrahydropyrylium, 2, and 2-ethoxy-3,4,4a,5,6,7,8,8a-octahydro-1-benzopyrylium, 3, hexachloroantimonates have been determined by X-ray crystallography. In each case the tetrahydropyrylium rings exist in shallow half-chair conformations with the cationic centers C(6), C(5), 0(1), and O(6) having a planar arrangement. The cations all have a Z conformation about the 0 ( 6 j C ( 7 ) bonds and it is shown that this conformation is also preferred in solution by comparison of narrow-line I3C NMR spectra in the solid state and solution. The O ( l W ( 2 ) and 0 ( 6 w ( 7 ) bond distances in 1-3 are significantly longer than those of comparable bonds in neutral esters. The length of the O ( l W ( 2 ) bond is very dependent on substitution at C(2) suggesting a considerable fraction of the positive charge resides on this carbon as well as C(7). The closest cationlanion interactions present in the crystal lattices of these salts are between the chlorine atoms of the anion and the cationic center, C(6). These interactions provide information on the origin of the stereoselectivity observed in nucleophilic attack on these cations. The conformations, details of the C-0 bonding, and closest contacts between cation and anion are discussed in terms of the concept of stereoelectronic control.Key words: 6-ethoxytetrahydropyrylium cations, lactonium salts, structure, X-ray, stereoelectronic control. Chem. 69, 2024Chem. 69, (1991.Les structures des hexachloroantimonates des 6-Cthoxy-2,3,4,5-tttrahydropyrylium (I), 6-tthoxy-2-mCthyl-2,3,4,5-tttrahydropyrylium (2) et 2-~thoxy-3,4,4a,5,6,7,8,8a-octahydro-l-benzopyrylium (3) ont Ct C dCterminCes par diffraction des rayons-X. Dans chaque cas, les cycles tCtrahydropyrylium existent dans des conformations demi-chaises peu profondes dans lesquelles les centres cationiques C(6), C(5), O(1) et O(6) sont dans un arrangement planaire. Les cations possbdent tous une conformation Z autour des liaisons 0 ( 6 w ( 7 ) ; par comparaison des bandes fines des spectres RMN du 13C i i 1'Ctat solide et en solution, on a aussi dtmontrC que cette conformation est aussi la conformation privilCgiCe en solution. Les longueurs des distances 0 ( 1 ) 4 ( 2 ) et O(6)-X(7) des composCs 1-3 sont beaucoup plus longues que celles des liaisons comparables des esters neutres. La longueur de la liaison O ( l W ( 2 ) dtpend beaucoup de la substitution en C(2); ce rCsultat suggkre qu'une fraction importante de la charge positive se trouve sur ce carbone ainsi que sur celui en C(7). Les interactions cation/anion le plus proches observCes dans les rCseaux cristallins de ces sels se retrouvent entre les atomes de chlore de l'anion et le centre cationique C(6). Ces interactions fournissent de l'information sur l'origine de la stCrCosClectivitC observCe lors des attaques nuclCophiles sur ces cations. On fait appel au concept de contr6le stCrCoClectronique pour discuter des conformations, des details de l...

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The Baeyer-Villiger Oxidation of Bicyclic Ketones

Cited by 78 publications

References 1 publication

100 Years of Baeyer–Villiger Oxidations

100 Years of Baeyer–Villiger Oxidations

Cyclization of Hydroxyenol Ethers into Spiroacetals. Evidence for the position of the transition state and its implication on the stereoelectronic effects in acetal formation

Structural studies on 6-ethoxytetrahydropyrylium cations; stereoelectronic control in the reactions of lactonium salts

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