Synthesis of 3-hydroxy-3-(hydroxymethyl)-5-methylcyclohexane-1,2-dione dibenzoate, a reported hydrolytic degradation product of leucogenenol

Aberhart, D. John; Clardy, Jon; Ghoshal, P. K.; He, Cun-Heng; Zheng, Qi‐Tai

doi:10.1021/jo00187a026

Cited by 5 publications

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“…The solvents were removed in vacuo to provide an oily residue that was purified by silica gel flash chromatography (hexanes/EtOAc 2:1; R f = 0.23 in hexanes/EtOAc 1:1) to afford the known compound 2-hydroxy-2-(hydroxymethyl)cyclohexanone as a colorless oil (0.66 g, 34%). The 1 H and 13 C NMR data for this material matched previously reported values. , …”

Section: Methodssupporting

confidence: 88%

“…The 1 H and 13 C NMR data for this material matched previously reported values. 39,40 (1-Hydroxy-2-oxocyclohexyl)methyl 2-Diazoacetate (7). 2-Hydroxy-2-(hydroxymethyl)cyclohexanone (5) (0.15 g, 1.03 mmol) in CH 2 Cl 2 (1 mL) was added to a 0 °C solution of p-toluenesulfonylhydrazone glyoxylic acid chloride (6) 28,41 (0.29 g, 1.14 mmol) in CH 2 Cl 2 (10 mL) to provide a light-yellow solution.…”

Section: ■ Conclusionmentioning

confidence: 99%

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Fragmentation of Bicyclic γ-Silyloxy-β-hydroxy-α-diazolactones as an Approach to Ynolides

Bayır

Brewer

2014

J. Org. Chem.

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Medium-sized ynolides were prepared by the Lewis acid-mediated fragmentation of bicyclic γ-silyloxy-β-hydroxy-α-diazolactones in which the Cβ–Cγ bond is the ring fusion bond. Although these lactone fragmentation substrates reacted somewhat less efficiently than their carbocyclic counterparts, the fragmentation provided 11-membered ynolides in up to 84% yield. Unlike prior fragmentations of similar substrates, elevated temperatures were required to obtain optimum yields of the ynolide products. The ynolides reported herein have ring sizes of 10 or 11, which are the smallest reported to date.

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Section: Methodssupporting

confidence: 88%

Section: ■ Conclusionmentioning

confidence: 99%

Fragmentation of Bicyclic γ-Silyloxy-β-hydroxy-α-diazolactones as an Approach to Ynolides

Bayır

Brewer

2014

J. Org. Chem.

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“…3-(Benzoyloxy)-3-[(benzoyloxy)methyl]cyclohexane-1,2-dione 1878[1398]: Trifluoroacetic anhydride (104 mL, 155 mg, 0.74 mmol) was added over 5 min to a solution of dimethyl sulfoxide (70 mL, 77 mg, 0.99 mmol) in dry dichloromethane (1.1 mL) at À70 C under argon. Thus, oxidation of dibromobicycloheptenediol 1876 gave dibromobicycloheptenedione 1877 in 68% yield.Typical procedure.…”

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confidence: 99%

Phosgenation Reactions: Sections 4.5.3–4.8

2003

Phosgenations ‐ a Handbook

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Oxidation of Alcohols to Carbonyl Compounds via Alkoxysulfonium Ylides: TheMoffatt,Swern, and Related Oxidations

Tidwell

1990

Organic Reactions

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The use of dimethyl sulfoxide as an oxidizing agent began with the discoveries by Kornblum and co‐workers that certain α‐bromo ketones were converted into glyoxals under mild conditions by treatment with dimethyl sulfoxide, and that primary tosylates such as n ‐octyl tosylate were converted into the corresponding aldehydes using dimethyl sulfoxide and sodium bicarbonate at 150° for 3 minutes. The initial step of the reactions involves a displacement by dimethyl sulfoxide giving an alkoxysulfonium ion and this species undergoes a 1,2 elimination assisted by base to give the carbonyl product A few years later it was discovered that alcohols were oxidized at room temperature to carbonyl compounds by dimethyl sulfoxide, dicyclohexylcarbodiimide (DCC), and phosphoric acid. This reaction was immediately recognized as an effective and mild procedure for sensitive substrates, and the extensive studies by this group and the development of alternative variations elsewhere have been the subject of several earlier reviews. The course of the Moffatt procedure is summarized. The key intermediate in this process is the oxysulfonium ylide, which appears to be common to all of the variations of dimethyl sulfoxide oxidations, and which reacts intramolecularly to give the products. Other related procedures that were soon developed utilize dimethyl sulfoxide activated by acetic anhydride, phosphorus pentoxide, sulfur trioxide/pyridine complex, and chlorine. Reaction of alcohols with phosgene to give chloroformates which react with dimethyl sulfoxide to give alkoxysulfonium ions, followed by reaction with triethylamine, also effects oxidation. The reaction of the complexes of dimethyl sulfide and chlorine or N ‐chlorosuccinimide (NCS) with alcohols is proposed to give the same alkoxysulfonium complexes, which are efficiently converted into carbonyl products upon addition of triethylamine. Electrochemical activation of sulfides has also been successfully utilized. The activation of dimethyl sulfoxide is effected by many reagents, and these reactions as well as those involving activated sulfides evidently involve the alkoxysulfonium ion and the decisive oxidation step which occurs via the alkoxysulfonium ylide in all the reactions. Activation of dimethyl sulfoxide by oxalyl chloride, has become the most used of these oxidation procedures, but several of the other methods are also convenient and efficient.

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Synthesis of 3-hydroxy-3-(hydroxymethyl)-5-methylcyclohexane-1,2-dione dibenzoate, a reported hydrolytic degradation product of leucogenenol

Cited by 5 publications

References 0 publications

Fragmentation of Bicyclic γ-Silyloxy-β-hydroxy-α-diazolactones as an Approach to Ynolides

Fragmentation of Bicyclic γ-Silyloxy-β-hydroxy-α-diazolactones as an Approach to Ynolides

Phosgenation Reactions: Sections 4.5.3–4.8

Oxidation of Alcohols to Carbonyl Compounds via Alkoxysulfonium Ylides: TheMoffatt,Swern, and Related Oxidations

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