Synthesis of a mixture of (2S,5R)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane, the odor bouquet minor components of Paravespula vulgaris (L.), from l-sorbose

Cubero, Isidoro Izquierdo; López-Espinosa, Maria T. Plaza; Kari, Naama

doi:10.1016/0008-6215(94)00320-f

Cited by 16 publications

(4 citation statements)

References 20 publications

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“…Finally, it should be noted that reaction of L ‐sorbose ( 1 ) with potassium thiocyanate gives analogous compound bearing a nitrogen function in the anomeric position (Scheme ) 21d…”

Section: Preparation Of Furanose/furanoside Derivativesmentioning

confidence: 99%

The Chemistry of L‐Sorbose

Zebiri

Balieu

Guilleret³

et al. 2011

Eur J Org Chem

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“…Finally, it should be noted that reaction of L ‐sorbose ( 1 ) with potassium thiocyanate gives analogous compound bearing a nitrogen function in the anomeric position (Scheme ) 21d…”

Section: Preparation Of Furanose/furanoside Derivativesmentioning

confidence: 99%

The Chemistry of L‐Sorbose

Zebiri

Balieu

Guilleret³

et al. 2011

Eur J Org Chem

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“…We followed a protecting group strategy to isolate and then oxidize the hydroxyl group at C6 (Scheme ). The synthesis began with the benzylation of the primary alcohol at C1, followed by the selective deprotection of the less stable isopropylidene acetal under aqueous acidic conditions, in the presence of acetone, to afford the diol 8 in 97% yield from 6 . Benzylation of the secondary hydroxyl group was performed by way of the temporary protection of the primary hydroxyl group of 8 as a trityl ether, benzylation of the secondary OH and cleavage of the trityl group using HBr in glacial acetic acid.…”

Section: Resultsmentioning

confidence: 99%

“…1- O -Benzyl-2,3:4,6-di- O -isopropylidene- α - l -sorbofuranose (7). To a stirred solution of 6 (40 g, 150 mmol) in anhydrous THF (40 mL) was added NaH (12.5 g, 312.5 mmol) at 0 °C. After 30 min at room temperature, benzyl bromide (30 mL, 250 mmol) and tetrabutylammonium iodide (3 g, 10 mmol) were added.…”

Section: Methodsmentioning

confidence: 99%

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A General Strategy for the Practical Synthesis of Nojirimycin C-Glycosides and Analogues. Extension to the First Reported Example of an Iminosugar 1-Phosphonate

et al. 2002

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An efficient and versatile strategy for the synthesis of nojirimycin C-glycosides and related compounds with full stereocontrol is reported. The key steps of the process are the addition of organometallic reagents onto an L-sorbose-derived imine (13) followed by an internal reductive amination. The addition step, which controls the alpha- vs beta-configuration at the pseudoanomeric center in the final product, is highly diastereoselective (re-face addition), and the stereoselectivity can be effectively inverted by adding an external monodentate Lewis acid (si-face addition). The complete synthesis could be achieved in 10 steps only from commercially available 2,3;4,6-di-O-isopropylidene-alpha-L-sorbofuranose and provided alpha- or beta-1-C-substituted 1-deoxynojirimycin derivatives in 27-52% overall yield. The strategy was successfully extended to the first example of an iminosugar 1-phosphonate. The methodology provides access to a wide range of biologically relevant glycoconjugate mimetics in which the glycosidic function is replaced by an imino-C-glycosidic linkage.

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The Barton‐McCombie Reaction

2012

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Deoxygenations of alcohols, i.e., processes that replace a hydroxyl group with hydrogen at a saturated carbon, find applications in both total synthesis and the systematic modifications of natural products. They may also be employed to introduce deuterium or tritium in a site‐specific manner. Reductive methods that involve ionic or highly polarized reagents or intermediates can be limited in their applicability: for example, competing reaction pathways including cationic rearrangements and anionic eliminations may be encountered in sterically hindered systems with substrates bearing heteroatoms close to the center undergoing reduction. As evidenced by developments over the last few decades, methods that involve the generation and direct quenching via hydrogen atom abstraction of the derived, carbon‐centered radical typically show the greatest tolerance for the presence of other functional groups and for variations in both the steric acid and the electronic environment in the vicinity of the center undergoing deoxygenation. Derivatization of the hydroxyl is a prerequisite, the determinant factors for efficient formation of the deoxygenated product lies in the ability of the combination of the substrate and reagents to induce homolysis of the C‐O bond coupled with the induction of homolysis to rapidly reduce a free radical by hydrogen donation, thereby propagating an efficient chain process. A high‐yielding way to realize this sequence was first described by Barton McCombie using the free‐radical chain reaction of O ‐thioacyl derivatives of secondary alcohols with tri‐ n ‐butylstannane. This chapter provides a detailed description and comparison of the combinations of substrates and reagents that will bring about these processes and provides a summary and evaluation of alternative deoxygenation methods. Mechanistic and stereochemical issues set out the scope and limitations of these processes with respect to both the thioacylation and reduction steps and exemplify some applications to both total synthesis and the modification of natural products.

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Synthesis of a mixture of (2S,5R)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane, the odor bouquet minor components of Paravespula vulgaris (L.), from l-sorbose

Cited by 16 publications

References 20 publications

The Chemistry of L‐Sorbose

The Chemistry of L‐Sorbose

A General Strategy for the Practical Synthesis of Nojirimycin C-Glycosides and Analogues. Extension to the First Reported Example of an Iminosugar 1-Phosphonate

The Barton‐McCombie Reaction

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