Oxidative Spaltung von 3‐Alkoxy‐2,5‐dihydrofuranen und ihre Anwendung in der De‐novo‐Synthese seltener Monosaccharide am Beispiel von <scp>L</scp>‐Cymarose

Brasholz, Malte; Reißig, Hans‐Ulrich

doi:10.1002/ange.200604078

Cited by 11 publications

(2 citation statements)

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“…In our synthetic concept we employ lithiated alkoxyallenes16,17 for the efficient and stereocontrolled elongation of carbohydrate‐derived nitrones by three functionalized carbon atoms. This leads to enantiopure 3,6‐dihydro‐2 H ‐1,2‐oxazines C as relay intermediates, which can be used for a manifold of subsequent reactions.…”

Section: Discussionmentioning

confidence: 99%

Acid‐Induced and Reductive Transformations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives

et al. 2008

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Acid‐catalyzed transformations of carbohydrate‐derived 3,6‐dihydro‐2H‐1,2‐oxazines such as 1, 5 and 13 provided a set of enantiopure furano‐1,2‐oxazines or pyrano‐1,2‐oxazines. The reaction conditions determined the degree of solvolysis of the compounds. An X‐ray analysis of product 6 revealed an interesting network of hydrogen bonds. Reductive cleavage of the N–O bond of the 1,2‐oxazines either by hydrogen/palladium or by samarium diiodide furnished enantiopure aminofuran and ‐pyran derivatives, e.g. 9 and 11 or compound 16, which can be regarded as protected 4‐amino‐1,4‐dideoxyhex‐3‐ulose or 4‐amino‐1,4‐dideoxyoct‐3‐ulose derivatives. We thus have established a short and stereocontrolled route to amino carbohydrate derivatives with 1,2‐oxazines as crucial relay compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Discussionmentioning

confidence: 99%

Acid‐Induced and Reductive Transformations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives

et al. 2008

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“…[60] Reissig and Brasholz reported ad en ovo synthesis of l-cymarose via dihydropyran intermediate B (Scheme 24). [61] The key step is also DDQ-mediated oxidative rearrangement. The dihydrofurani ntermediate A was oxidized to form dihydropyran intermediate B,i naprocess that was very mechanistically similar to that of Achmatowicz rearrangement.…”

Section: Formation Of Dihydropyrans By Othermethodsmentioning

confidence: 99%

De Novo Synthesis of Mono‐ and Oligosaccharides via Dihydropyran Intermediates

Song

Wang

Tang

2017

Chemistry An Asian Journal

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The importance of carbohydrates is evident by their essential role in all living systems. Their syntheses have attracted attention from chemists for over a century. Most chemical syntheses in this area focus on the preparation of carbohydrates from naturally occurring monosaccharides. De novo chemical synthesis of carbohydrates from feedstock starting materials has emerged as a complementary method for the preparation of diverse mono- and oligosaccharides. In this review, the history of de novo carbohydrate synthesis is briefly discussed and particular attention is given to methods that address the formation of glycosidic bonds for potential de novo synthesis of oligosaccharides. Almost all methods of this kind involve the formation of dihydropyran intermediates. Recent progress in forming dihydropyrans by Achmatowicz rearrangement, hetero-Diels-Alder cycloaddition, ring-closing metathesis, and other methods is also elaborated.

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Reactions of Cycloaliphatic Thioketones and Their Oxo Analogues with Lithiated Methoxyallene: A New Approach to Vinylthiiranes

Jasiński

Mlostoń

Stolarski

et al. 2014

Chemistry An Asian Journal

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Admantanethione smoothly reacted with lithiated methoxyallene at low temperatures yielding the expected allenyl-substituted thiolate, which upon aqueous work-up underwent spontaneous 1,3-cyclization to afford a hitherto unknown methoxy-substituted vinylthiirane derivative. The analogous reaction with adamantanone led to the corresponding allenyl alcohol that can be isolated and--depending on the conditions applied--either be converted into the corresponding vinyloxirane or into the 2,5-dihydrofuran derivative. Sterically more crowded thioketones were also combined with lithiated methoxyallene, but in these cases competitive 1,5-cyclization leading to isomeric dihydrothiophene derivatives was observed. DFT calculations of model intermediates and products show distinct energy differences of the sulfur and the corresponding oxygen compounds. Desulfurization of the adamantanethione-derived vinylthiirane yielded a methoxy-substituted 1,3-diene that was studied in cycloadditions with electron-deficient dienophiles. Whereas in the case of tetracyanoethylene the corresponding cyclobutane derivative was formed, the reaction with nitrosobenzene provided the expected 1,2-oxazine derivative. By reductive cleavage of the N-O bond this heterocycle was converted into an unsaturated amino alcohol bearing an adamantane moiety.

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Oxidative Spaltung von 3‐Alkoxy‐2,5‐dihydrofuranen und ihre Anwendung in der De‐novo‐Synthese seltener Monosaccharide am Beispiel von L‐Cymarose

Cited by 11 publications

References 43 publications

Acid‐Induced and Reductive Transformations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives

Acid‐Induced and Reductive Transformations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives

De Novo Synthesis of Mono‐ and Oligosaccharides via Dihydropyran Intermediates

Reactions of Cycloaliphatic Thioketones and Their Oxo Analogues with Lithiated Methoxyallene: A New Approach to Vinylthiiranes

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Oxidative Spaltung von 3‐Alkoxy‐2,5‐dihydrofuranen und ihre Anwendung in der De‐novo‐Synthese seltener Monosaccharide am Beispiel von L‐Cymarose

Cited by 11 publications

References 43 publications

Acid‐Induced and Reductive Transfor­mations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives

Acid‐Induced and Reductive Transfor­mations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives

De Novo Synthesis of Mono‐ and Oligosaccharides via Dihydropyran Intermediates

Reactions of Cycloaliphatic Thioketones and Their Oxo Analogues with Lithiated Methoxyallene: A New Approach to Vinylthiiranes

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Product

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Acid‐Induced and Reductive Transformations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives

Acid‐Induced and Reductive Transformations of Enantiopure 3,6‐Dihydro‐2H‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives