Synthesis of gamma-hydroxy enones via persulfate oxidation of dienyl ethers.

Suryawanshi, S. N.; Fuchs, P. L.

doi:10.1016/s0040-4039(01)82104-3

Cited by 30 publications

(3 citation statements)

References 14 publications

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“…The following reduction by DIBAL in THF gave the regioisomers mixture 12 of enol derivatives that was further oxidized to the isomeric epoxy-alcohols 13 by 3-chloroperoxybenzoic acid (MCPBA). In another reaction, the isomeric enones 11a / 11b were acetylated giving rise to the corresponding enols 14 which were then oxidized at the allylic position by Oxone ® [ 18 ] obtaining the regioisomeric mixture 15 that was further purified giving compounds 15a and 15b .…”

Section: Resultsmentioning

confidence: 99%

“…Mixture of Compounds 15a and 15b : Mixture 11 (70 mg, 0.23 mmol), N , N -dimethylaminopyridine (3.1 mg, 0.025 mmol), triethylamine (0.051 g, 0.51 mmol) and acetic anhydride (0.126 g, 1.26 mmol) were stirred for 18 h at 70 °C; the mixture was partitioned between diethylether and ammonium bicarbonate (10%) and the organic phase was purified by silica-gel column using a gradient of petroleum ether/diethylether to obtain the acetate intermediate 14 [ 18 ], that was dissolved in methanol (0.5 mL) and sodium bicarbonate (saturated) buffer solution (0.5 mL) of Oxone ® (0.052 mmol); after stirring at 25 °C for 7 h, methanol (0.5 mL), water (0.5 mL) and oxone (0.052 mmol) were added and the mixture was kept under stirring overnight; after partition between water and chloroform, the organic phase was purified by silica-gel column using a gradient of petroleum ether and diethylether to give 15 as a mixture of regioisomers (9 mg, 0.0276 mmol, 12%); R f (Petroleum ether/diethyl ether 6/4) = 0.1; 1 H-NMR (400 MHz, C 6 D 6 ): δ = 6.64 (dd, J = 15.7, 4.5 Hz, 1H), 6.23 (dd, J = 15.7, 1.4 Hz, 1H), 3.79 (m, 1H), 3.39 (s, 3H; OCH 3 ), 2.28 (t, J = 7.2 Hz, 2H), 2.06 (t, J = 7.2 Hz, 2H; H2), 1.69 (m, 2H), 1.51 (m, 2H), 1.30-1.11 (m, 16H), 0.89 (t, J = 6.2, 3H; H 3 18); 13 C-NMR (100MHz, C 6 D 6 ): δ = 199.2 (C), 147.2 (CH), 128.0 (CH), 70.9 (CH), 51.0 (OCH 3 ), 41.03 (CH 2 ), 36.7 (CH 2 ), 33.9 (CH 2 ), 32.1 (CH 2 ), 30.3 (CH 2 ), 29.8 (CH 2 ), 29.6 (CH 2 ), 29.1 (CH 2 ), 25.1 (2 CH 2 ), 24.4 (CH 2 ), 23.0 (CH 2 ), 14.3 (CH 3 ). UV λ max (MeOH) 219 nm (ε = 1570); HRMS (ESI + ): m/z calcd for C 19 H 34 O 4 Na: 349.2355; found: 349.2359.…”

Section: Methodsmentioning

confidence: 99%

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Design and Synthesis of Pro-Apoptotic Compounds Inspired by Diatom Oxylipins

et al. 2013

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Oxylipins are a large and diverse family of fatty acid derivatives exhibiting different levels of oxidation of the carbon chain. They are involved in many biological functions in mammals, plants and diatoms. In this last group of organisms, they are suggested to play a role in the reproductive failure of copepod predators, showing clear pro-apoptotic effects on newborn nauplii. In this work, these compounds were tested for the ability to induce mitotic arrest in sea urchin embryos. We show for the first time that oxylipins have an increased efficacy in their corresponding methylated form. Natural oxylipins were also used as an inspiration for the rational design and synthesis of stable chemical analogs with apoptotic activity against tumor cell lines. This approach led to the synthesis of the linear C15-ketol (22) that was shown to induce apoptosis in human leukemia U-937 cells. These results are proof of the concept of the use of eco-physiological considerations as a platform to guide the search for novel drug candidates.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Design and Synthesis of Pro-Apoptotic Compounds Inspired by Diatom Oxylipins

et al. 2013

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“…Although use of m -CPBA resulted in rather complex results, OXONE in acetone−water 10d, was found to give the desired labile epoxide which was converted into diol 18 by exposure to acetic acid (Scheme ). It should be noted that no product arising from Baeyer−Billiger reaction or epoxidation at the A ring was detected, probably because the highly strained C6−C7 double bond is much more reactive than the C4−C5 double bond 7 …”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of (−)-Coriolin

et al. 1999

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An efficient synthetic method for (-)-coriolin has been developed on the basis of a [3+2] cycloaddition reaction of a 1-(methylthio)-2-siloxyallyl cationic species and vinylsulfides. An enantiomerically pure C-ring unit was prepared through optical resolution of five-membered allyl ester 6b using a lipase. The first [3+2] cycloaddition reaction of C-ring unit (S)-7 gave bicyclic ketones 8 and 9, which were easily converted into vinyl sulfide 11. Stereoselective construction of the A-ring was achieved by the second [3+2] cycloaddition reaction of the BC-ring unit. New methods for introduction of the oxygen functional groups to the triquinane skeleton were also developed for the last stages of the total synthesis. Thus, the C7 hydroxyl group was introduced by epoxidation of dienol silyl ether 17, and stereocontrolled construction of the spiro epoxide moiety was accomplished on the basis of a Darzens-type reaction.

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α‐Hydroxylation of Enolates and Silyl Enol Ethers

et al. 2003

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The autoxidation of enolizable carbonyl compounds was reported as early as 1871, and the accelerating action of base is well documented. The products of these reactions, however, were usually mixtures of compounds resulting from decomposition of the unstable alpha‐hydroperoxy intermediates. It was not recognized until the 1960s that these intermediates can be reduced to alpha‐hydroxy compounds with zinc dust. This observation laid the foundation for what has become on of the simplest and most widely used strategies for introducing a hydroxyl group adjacent to a carbonyl group, namely the oxidation of metal enolates. The alpha‐hydroxy carbonyl array not only occurs in many biologically active molecules, but also serves as an important building block for synthesis. While the oxygenation of enolates still play an important role in the synthesis of alpha‐hydroxy carbonyl compounds, a variety of new, more convenient oxididizing agents, including chiral nonracemic ones, have been introduced. In addition, sily enol ethers and silyl ketene acetals can serve as educts for alpha‐hydroxycarbonyl compounds. This chapter covers the literature of alpha‐hydroxylation of metal enolates and silyl enol ethers up to the end of 2000. Nitriles and aza‐enolates are included. The related alpha‐alkoxylation, alpha‐acyloxylation, and alpha‐sulfonyloxylation of metal enolates are briefly discussed.

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Synthesis of gamma-hydroxy enones via persulfate oxidation of dienyl ethers.

Cited by 30 publications

References 14 publications

Design and Synthesis of Pro-Apoptotic Compounds Inspired by Diatom Oxylipins

Design and Synthesis of Pro-Apoptotic Compounds Inspired by Diatom Oxylipins

Total Synthesis of (−)-Coriolin

α‐Hydroxylation of Enolates and Silyl Enol Ethers

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