Diastereoselective synthesis of new O-alkylated and C-branched inositols and their corresponding fluoro analogues

Collet, Charlotte; Chrétien, Françoise; Chapleur, Yves; Lamandé‐Langle, Sandrine

doi:10.3762/bjoc.12.39

Cited by 5 publications

(2 citation statements)

References 49 publications

(42 reference statements)

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“…In particular, it has been proven that the axial OH group β to the keto function plays a fundamental role in directing the nucleophilic attack [45–47]. It has also to be mentioned that by changing the experimental conditions (temperature and alcoholic solvent) a different diastereoselectivity has been reported in the reduction of the same protected inosose [45,48]. This highlights how subtle changes in the inosose structure and/or in the experimental conditions affect the stereo-outcome of the reduction.…”

Section: Resultsmentioning

confidence: 99%

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

D’Andrea

Catelani

Guazzelli

et al. 2016

Beilstein J. Org. Chem.

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The intramolecular aldol condensation of aldohexos-5-ulose derivatives of the D-xylo and L-ribo stereoseries has been studied. Only one of the four possible inososes was isolated from both stereoseries in reasonable yields (30–38%). The results obtained, together with the previous findings for the L-arabino and L-lyxo stereoseries, allowed for the rationalisation of a mechanism of the reaction based on open-transition-state models and electron-withdrawing inductive effects. Complementary reductions of the intermediate inososes were possible by changing the reaction conditions, and two isomeric inositol derivatives were obtained with complete stereoselection from each inosose. The presented approach permits us to control the configuration of three out of the six stereocentres of the inositol frame and gives access to seven of the nine inositols. Noteworthy, for the D-xylo derivative, the two-step sequence (condensation followed by reduction with NaBH(OAc)3) represents the biomimetic synthesis of myo-inositol. Furthermore, the sugar-based pathway leads directly to enantiomerically pure selectively protected inositols and does not require any desymmetrisation procedure which is needed when myo-inositol and other achiral precursors are employed as starting materials. As an example of application of the method, the indirect selective protection of secondary inositols’ hydroxy functions, by placing specific protecting groups on the aldohexos-5-ulose precursor has been presented.

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Section: Resultsmentioning

confidence: 99%

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

D’Andrea

Catelani

Guazzelli

et al. 2016

Beilstein J. Org. Chem.

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“…The acetylation of the somewhat fragile tertiary chloromethyl propargylic alcohols 12 proved to be unexpectedly challenging, and numerous methods had to be screened. Ultimately, the most effective procedure was the acid-catalyzed acetyl exchange with 2-propenyl acetate . Route B could be applied for the case where R 3 ≠ H through reaction of lithium acetylide derived from pivalate 13 with the appropriate aldehyde (Piv = pivalate).…”

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confidence: 99%

Sigmatropic Rearrangement-Based Synthesis of 4-Alkenyl-1,3-dithiol-2-ones

2019

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A series of conjugated 4-alkenyl-1,3-dithiol-2-ones have been prepared by microwave-assisted rearrangement of S-(4-acyloxy-2-alkynyl)-O-ethyl xanthates in moderate to good yields. The synthetic approach is based on a combination of [3,3] and [1,5] sigmatropic rearrangements as well as the intermediacy of a reactive betaine that induces the ionic elimination of the acyloxy group. The [1,5] sigmatropic rearrangement was confirmed by a deuterium-labeling experiment.

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Isopropenyl Esters (iPEs) in Green Organic Synthesis

Rigo

Masters

Maschmeyer

et al. 2022

Chemistry A European J

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The need for greener compounds able to replace conventional ones with similar reactivity is crucial for the development of sustainable chemistry. Isopropenyl esters (iPEs) represent one eco-friendly alternative to acyl halides and anhydrides. This review provides a comprehensive overview of the preparation methodologies and reported synthetic applications of iPEs and, in particular, of isopropenyl acetate (iPAc). Intriguingly, the presence of a C=C double bond adjacent to the ester functionality makes iPEs appealing in different chemoselective organic synthesis transformations. For instance, the acyl moiety is suitable for transesterification reactions in presence of different heteroatom-based nucleo-philes (CÀ , OÀ , NÀ , SÀ , SeÀ ); these reactions are irreversible thanks to the formation of acetone, obtained upon keto-enol tautomerization of the prop-1-en-2-ol (isopropenyl) leaving group. Similarly, the unsaturation contained in the isopropenyl synthon could be selectively exploited in organic synthesis for electrophilic and/or radical additions as well as in metal-catalyzed cross-coupling reactions. To conclude, iPEs recently found major interest in the direct modification of biomass (i.e. lignin or cellulose) and in the implementation of tandem reactions of esterification-acetalization by exploiting the co-formation of acetone during the reaction.

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Diastereoselective synthesis of new O-alkylated and C-branched inositols and their corresponding fluoro analogues

Cited by 5 publications

References 49 publications

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

Sigmatropic Rearrangement-Based Synthesis of 4-Alkenyl-1,3-dithiol-2-ones

Isopropenyl Esters (iPEs) in Green Organic Synthesis

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