Glycosylated vinyl ethers by the Julia–Lythgoe–Kocienski olefination: application to the synthesis of 2′,5′-dideoxydisaccharides and carbohydrated β-lactams

Sánchez, Iván Pérez; Turos, Edward

doi:10.1016/j.tetasy.2009.05.039

Cited by 15 publications

(1 citation statement)

References 55 publications

(7 reference statements)

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“… 6 A multistep synthetic route for acyclic disubstituted vinylic ethers via alkynyl ethers ( 2 ) provides each ( E )- and ( Z )-isomer ( 3 , 4 ) from primary and secondary alcohols, but with limited functionality in the vinylic sector ( Figure 1 a). 7 Other methods for acyclic disubstituted vinylic ethers have limited scope 8 or poor stereoselectivity, 9 restricting potential applications. Intermolecular single-step C–O bond cross-couplings provide aromatic ethers from phenols and/or aromatic synthons, 10 , 11 but corresponding syntheses of substituted vinylic ethers from less acidic sp 3 -hybridized alcohols and substituted vinylic synthons are not well developed.…”

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Stereospecific Cu(I)-Catalyzed C–O Cross-Coupling Synthesis of Acyclic 1,2-Di- and Trisubstituted Vinylic Ethers from Alcohols and Vinylic Halides

2023

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CuI and trans-N,N′-dimethylcyclohexyldiamine catalyze the single-step C–O bond cross-coupling between 1,2-di- and trisubstituted vinylic halides with functionalized alcohols, producing acyclic vinylic ethers. This stereospecific transformation selectively gives each of the (E)- and (Z)-vinylic ether products from the corresponding vinyl halide precursors. This method is compatible with carbohydrate-derived primary and secondary alcohols and several other functional groups. The conditions are mild enough to reliably generate vinylic allylic ethers without promoting Claisen rearrangements.

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confidence: 99%

Stereospecific Cu(I)-Catalyzed C–O Cross-Coupling Synthesis of Acyclic 1,2-Di- and Trisubstituted Vinylic Ethers from Alcohols and Vinylic Halides

2023

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TheJulia–Kocienski Olefination

Blakemore¹,

Sephton

Ciganek

2018

Organic Reactions

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The Julia–Kocienski olefination is a direct connective synthesis of alkenes via the addition of metalated aryl alkyl sulfones to carbonyl compounds. The activating aromatic group associated with the sulfone must possess electrophilic character, and alkene formation occurs via β‐alkoxy sulfone formation, transfer of the aryl group from sulfur to oxygen via a Smiles rearrangement, and then elimination of sulfur dioxide and an aryloxide anion from the resulting β‐aryloxy sulfinate anion. The olefination process itself and the methods used to prepare the requisite sulfone substrates are tolerant of a wide variety of functional groups, and a variety of alkene targets can be prepared. Stereoselectivity is dependent on the nature of the sulfone, the carbonyl compound, the activating aryl moiety, and the reaction conditions. This chapter describes theoretical and operational aspects of the Julia–Kocienski olefination such that the reader will be able to obtain optimal results in his/her own research. A detailed mechanistic overview is included to account for the factors that influence stereoselectivity and yield. Methods for introducing sulfone activators into fragments of interest, best practices for generating sulfone anions, and optimal strategies for targeting different classes of alkene targets are discussed. Functional group compatibilities, reaction variants, and a comparison to other methods of alkene synthesis are also presented. Tabular surveys are organized according to type of alkene synthesized, with an emphasis on the degree of substitution and the level of conjugation about the newly formed double bond. The literature is covered from the initial disclosure of the Julia–Kocienski olefination in 1991 to the first quarter of 2016.

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Dihydropyrans by Cycloadditions of Oxadienes

et al. 2020

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3,4‐Dihydro‐2H‐pyrans are present in the skeletons of several natural products, and these versatile synthetic intermediates are readily transformed into tetrahydropyrans, pyridines, or 1,5‐dicarbonyl units. Among the strategies developed to access 3,4‐dihydro‐2H‐pyrans, the hetero‐Diels‐Alder reaction between an oxadiene and a dienophile is particularly valuable because up to three contiguous stereogenic centers can be created diastereo‐ and/or enantioselectively in a single step. This review addresses the mechanism of the reaction and presents methods for preparing the product dihydropyrans enantio‐ and diastereoselectively. Thermal and Lewis acid promoted cycloadditions are discussed, as is the role of activating groups on the oxadiene.

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Glycosylated vinyl ethers by the Julia–Lythgoe–Kocienski olefination: application to the synthesis of 2′,5′-dideoxydisaccharides and carbohydrated β-lactams

Cited by 15 publications

References 55 publications

Stereospecific Cu(I)-Catalyzed C–O Cross-Coupling Synthesis of Acyclic 1,2-Di- and Trisubstituted Vinylic Ethers from Alcohols and Vinylic Halides

Stereospecific Cu(I)-Catalyzed C–O Cross-Coupling Synthesis of Acyclic 1,2-Di- and Trisubstituted Vinylic Ethers from Alcohols and Vinylic Halides

TheJulia–Kocienski Olefination

Dihydropyrans by Cycloadditions of Oxadienes

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