General Synthesis of α-Acetoxy Ethers from Esters by DIBALH Reduction and Acetylation

Dahanukar, Vilas H.; Rychnovsky, S. D.

doi:10.1021/jo961205m

Cited by 165 publications

(87 citation statements)

References 18 publications

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“…Nucleophilic substitution reactions of the oxocarbenium ions were performed using acetate precursors obtained by reductive acetylation68 of the corresponding lactones prepared earlier (vide supra) . Although the acetates were typically obtained as mixtures of anomers, the anomer distributions did not affect the outcome of the substitution reactions 69.…”

Section: Experimental Approachmentioning

confidence: 99%

The Effect of Electrostatic Interactions on Conformational Equilibria of Multiply Substituted Tetrahydropyran Oxocarbenium Ions

2008

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The three-dimensional structures of dioxocarbenium ions related to glycosyl cations were determined by an analysis of spectroscopic, computational, and reactivity data. Hypothetical low-energy structures of the dioxocarbenium ions were correlated with both experimentally determined 1 H NMR coupling constants and diastereoselectivity results from nucleophilic substitution reactions. This method confirmed the pseudoaxial preference of C-3 alkoxy-substituted systems and revealed the conformational preference of the C-5 alkoxymethyl group. Although the monosubstituted C-5 alkoxymethyl substituent preferred a pseudoequatorial orientation, the C-5-C-6 bond rotation was controlled by an electrostatic effect. The preferred diaxial conformer of the trans-4,5-disubstituted tetrahydropyranyl system underscored the importance of electrostatic effects in dictating conformational equilibria. In the 2-deoxymannose system, although steric effects influenced the orientation of the C-5 alkoxymethyl substituent, the all-axial conformer was favored because of electrostatic stabilization.

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Section: Experimental Approachmentioning

confidence: 99%

The Effect of Electrostatic Interactions on Conformational Equilibria of Multiply Substituted Tetrahydropyran Oxocarbenium Ions

2008

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“…[12,13] Since the 1980s, aluminum acetals have found some applications in organic synthesis. In particular, they have been trapped with electrophiles, such as silyl triflates and silyl imidazole or acetic anhydride and acid fluorides to give the corresponding monosilyl acetals [14][15][16] and a-acetoxy acetals, [17,18] respectively. The latter were found to be very efficient for the generation of oxacarbenium ions, which could engage further in Prins [19] and oxonia-Cope [20] rearrangements or could be trapped by various nucleophiles.…”

Section: Introductionmentioning

confidence: 99%

Radical Cyclization of α‐Bromo Aluminum Acetals onto Alkenes and Alkynes (Radic[Al] Process): A Simple Access to γ‐Lactols and 4‐Methylene‐γ‐Lactols

Boussonnière

Bénéteau

Zimmermann

et al. 2011

Chemistry A European J

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An efficient preparation of γ-lactols and methylene-γ-lactols is described. Highly acid-sensitive lactols are prepared in a concise manner by using a radical cyclization of aluminum acetals. The precursors for the radical reactions are readily prepared from allyl or propargyl alcohols and α-bromo acids. Functionalization of the resulting γ-lactols and methylene-γ-lactols can be achieved following isolation, leading to synthetically useful building blocks, such as 1,4-diols, 1,4-dienes, γ-lactones, and polysubstituted tetrahydrofurans.

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“…[13] (H 2 L ¼ 2,6-bis(2-hydroxy-2,2-diphenylethyl)pyridine, prepared as described in ref. [15]) with TFAA and the silyl enol ethers shown in Table 1 under the conditions similar to those for 1 a/1 b but obtained no amination products from the reaction mixtures. …”

mentioning

confidence: 82%

Stereocontrolled Total Synthesis of (+)‐Leucascandrolide A

Paterson

Tudge

2003

Angewandte Chemie

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Weil die natürliche Quelle versiegt ist – die Rede ist vom Schwamm Leucascandra caveolata –, erscheinen Totalsynthesen des biologisch hoch wirksamen Leucascandrolid A (1) um so dringender. Bei der hier vorgestellten Synthese dieses strukturell einzigartigen Makrolids wird eine asymmetrische Jacobsen‐Hetero‐Diels‐Alder‐Reaktion für den Aufbau des Tetrahydropyranrings genutzt. Die Endphase der Synthese wird maßgeblich durch zwei Mitsunobu‐Reaktionen bestimmt, eine für den Ringschluss zum 18‐gliedrigen Makrolacton und eine zur Anbringung der Seitenkette mit dem Oxazolring.

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General Synthesis of α-Acetoxy Ethers from Esters by DIBALH Reduction and Acetylation

Cited by 165 publications

References 18 publications

The Effect of Electrostatic Interactions on Conformational Equilibria of Multiply Substituted Tetrahydropyran Oxocarbenium Ions

The Effect of Electrostatic Interactions on Conformational Equilibria of Multiply Substituted Tetrahydropyran Oxocarbenium Ions

Radical Cyclization of α‐Bromo Aluminum Acetals onto Alkenes and Alkynes (Radic[Al] Process): A Simple Access to γ‐Lactols and 4‐Methylene‐γ‐Lactols

Stereocontrolled Total Synthesis of (+)‐Leucascandrolide A

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