Novel method for the degradation of the carbon chain of organic acids and their derivatives

Fétizon, M.; Kakis, Frederic J.

doi:10.1021/jo00949a025

Cited by 11 publications

(3 citation statements)

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“…13 C NMR (100 MHz CDCl 3 ): δ = 198.5, 197.2, 145.2, 141.5, 140.7, 138.4, 137.3, 136.8, 136.1, 133.4, 132.5, 131.8, 129.57, 129.55, 129.4, 128.60, 128.56, 128.1, 128.0, 127.5, 127.3, 125.9, 31.63, 31.61, 29.9, 29.5, 29.3, 29.2, 29.1, 29.0, 28.93, 28.91, 22.5, 14.0 ppm. The 1 H NMR spectrum was consistent with reported data …”

Section: Methodssupporting

confidence: 90%

Olefination with Sulfonyl Halides and Esters: E‐Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors

et al. 2018

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Carbanions of sulfonyl halides and activated sulfonates add to carbonyl compounds, and so‐formed aldol‐type adducts spontaneously fragment into olefins. This transformation mimics the one‐pot Julia olefination with (hetero)aryl sulfones, but the mechanism of fragmentation involves a four‐membered intermediate, typical for reactivity of phosphorus reagents. Moreover, in contrast to the reactions of sulfones, sulfonates of fluorinated alcohols (TFE and HFI) produce byproducts that are easily removed during workup. In our report, we focus on reactions of unstabilized and semistabilized carbanion precursors: alkylsulfonates, and allyl‐ and benzylsulfonates, respectively. In particular for semistabilized systems, olefins were synthesized as predominant E isomers in good yields. The presented studies reveal that optimal reaction conditions, including the type of base and alcohol groups of the sulfonates, are different depending on stabilization of the carbanion precursors and structure of the carbonyl substrates. The practical synthetic guide is supplemented with a discussion of the mechanism, based on reactivity studies of intermediates and identification of side‐products.

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Section: Methodssupporting

confidence: 90%

Olefination with Sulfonyl Halides and Esters: E‐Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors

et al. 2018

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“…The filtrate was dried over anhydrous sodium carbonate and evaporated. Chromatography of the residue on alumina, activity IV, and elution with cyclohexane gave a pale yellow oil whose distillation [150°( 0.05 Torr)] yielded 1.80 g of colorless liquid diester 9a: ir (neat) C=0 5.81 (s), C=C 6.11 (w), 6.31 (m), 6.50 µ (m); pmr (CC14) 1.68 [d, 3, J = 7.0 Hz, Ále of major (88%) isomer], 2.25 [d, S, J = 7.0 Hz, Me of minor (12%) isomer], 3.62, 3.82 (s, 3 each, methoxyls), 7.05 [d, 1, J = 5.0 Hz, C(5) ], 7.07 (q, 1, J = 7.0 Hz, olefinic H), 8.65 [d, 1, / = 5.0 Hz, C(6) ], 9.10 [s, 1, C(2) ]. (The liquid turned yellow and its purity decreased on storage.)…”

Section: Oh Experimental Sectionmentioning

confidence: 99%

General methods of synthesis of indole alkaloids. XII. Synthesis of dl-18,19-dihydroantirhine and methyl demethylilludinate

Wenkert¹,

Sprague²,

Webb³

1973

J. Org. Chem.

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5 '-7V-(O-Ethylcarbamoyl )-5 '-deoxythymidine 3'-Phosphate Disodium Salt (22).-5'-Amino-5'-deoxythymidine 3'-phosphate inner salt (19, 300 mg) and Na2C03 (310 mg) were dissolved in a mixture of methanol (4 ml) and water (4 ml) and the solution was stirred at 0°. Ethyl chloroformate (135 mg) was added dropwise over a period of 5 min. The reaction mixture was stirred for an additional 10 min at 0°. The course of the reaction was monitored by tic (cellulose tic sheets, pc system A) and showed one spot (B, 0.70), different from starting material (Bt 0.47). The reaction mixture was neutralized with 0.3 N HC1 solution and concentrated in vacuo to a small volume. Water was added and the solution was lyophilized to give 500 mg of crude 22. The product was purified by ppc (pc system A, 12 sheets of 3 MM paper) to afford 250 mg of homogeneous 22. Compound 22 was purified further by fractional precipitation from water-2-propanol mixtures. Five fractions were collected. Fraction 2 was dissolved in water (10 ml) and the solution was concentrated in vacuo (repeated three times). The residue was dissolved in water again and lyophilized to give 40 mg of pure 22: uv max 267 µ (« 9700), uv min 234 (e 2500), 250/260 (0.67/270 (0.98), 270/ 280(1.62).

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“…The conversion of a carboxylic acid (or derivative) to an aldehyde or ketone with loss of one carbon atom plays an important role in organic chemistry. 1,2 This degradation is an important tool in the structural elucidation and characterization of natural products. 3 It also allows carboxylic acid derivatives to serve as synthetic equivalents of other structural fragments.…”

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confidence: 99%

A Convenient Method for One Step Oxidative Decarboxylation by KMnO₄ in Non Aqueous Media

Ataei

2000

Journal of Chemical Research

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Novel method for the degradation of the carbon chain of organic acids and their derivatives

Cited by 11 publications

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Olefination with Sulfonyl Halides and Esters: E‐Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors

Olefination with Sulfonyl Halides and Esters: E‐Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors

General methods of synthesis of indole alkaloids. XII. Synthesis of dl-18,19-dihydroantirhine and methyl demethylilludinate

A Convenient Method for One Step Oxidative Decarboxylation by KMnO₄ in Non Aqueous Media

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Novel method for the degradation of the carbon chain of organic acids and their derivatives

Cited by 11 publications

References 0 publications

Olefination with Sulfonyl Halides and Esters: E‐Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors

Olefination with Sulfonyl Halides and Esters: E‐Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors

General methods of synthesis of indole alkaloids. XII. Synthesis of dl-18,19-dihydroantirhine and methyl demethylilludinate

A Convenient Method for One Step Oxidative Decarboxylation by KMnO4 in Non Aqueous Media

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A Convenient Method for One Step Oxidative Decarboxylation by KMnO₄ in Non Aqueous Media