Aminooxylation Horner–Wadsworth–Emmons Sequence for the Synthesis of Enantioenriched γ-Functionalized Vinyl Sulfones

Doherty, William; Evans, Paul

doi:10.1021/acs.joc.5b02556

Cited by 21 publications

(31 citation statements)

References 83 publications

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“…[10,14a,23] Previously we have reported an organocatalytic method to prepare optically active γ-azido-α, -unsaturated sulfones. [24] During this work a single-crystal X-ray structure for (S)-15 was obtained. From this it was clear that, in the solid-state, a conformer of the type E-12b was preferred.…”

Section: Resultsmentioning

confidence: 99%

Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides

et al. 2020

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Reported is the construction, and facile base-mediated conversation of ten differently substituted 3-azido E-vinyl sulfones (γ-azido-α,-unsaturated sulfones) into their isomeric vinyl azide counterparts. The requisite 3-azido E-vinyl sulfones were prepared from 3-bromo E-vinyl sulfones, which in turn were accessed from allyl sulfones via a bromination-elimination sequence. In relation to this a one-pot azidation-isomerisation sequence was developed which enabled the direct formation of the vinyl azides from the corresponding 3-bromo E-vinyl sulfones. Similarly, a convenient one-pot Horner-Wadsworth-Emmons olefination-isomerisation approach was utilised in or-[a] N.

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Section: Resultsmentioning

confidence: 99%

Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides

et al. 2020

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“…However, this still resulted in erosion of the stereochemical integrity to 63 % ee . Fortunately, our previous synthesis of alkyne 13 by using the Corey–Fuchs method delivers enantiopure material (Scheme ) . It is worth noting that some control over the reaction conditions in this two‐step sequence was necessary – in order to avoid loss of the Cbz group in the first step, and then gradual addition of n BuLi in the second step to avoid the formation of side‐product 19 .…”

Section: Resultsmentioning

confidence: 99%

“…As shown in Scheme , the synthesis of allylic azide 25 starts from Fmoc‐protected Weinreb amide 26 . Chemoselective reduction with LiAlH 4 at –78 °C gave amino aldehyde 27 in excellent yield, without the need for column chromatography.…”

Section: Resultsmentioning

confidence: 99%

“…Purification by column chromatography (cyclohexane/EtOAc, 3:1) gave alkyne (±)‐ 13 (343 mg, 77 %) as a white waxy solid, as a mixture of enantiomers. For an enantiopure synthesis, see ref …”

Section: Methodsmentioning

confidence: 99%

“…Based on this precedent, we were interested in probing what impact the replacement of the native peptide bond with a triazole would have on anti‐trypanosomal activity (i.e., compound 3 vs. compound 5 , Figure ). Recently, we explored an organocatalytic synthesis of compound 5 and its epimer …”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Evaluation of 1,2,3‐Triazole‐Containing Vinyl and Allyl Sulfones as Anti‐Trypanosomal Agents

et al. 2017

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An approach is described to access 1,2,3‐triazole‐derived peptidyl vinyl sulfones as Trypanosoma brucei brucei inhibitors by using click chemistry, starting from a common azide intermediate. Among the triazole analogues, biotinylated inhibitors 11 and 12 offer possibilities as probes for the elucidation of target proteases for this compound class. The development of two syntheses of a 1,2,3‐triazole‐based vinyl sulfone 5 are also presented. This compound was accessed through a click reaction of a lysine‐derived azide (itself accessed by diazo transfer), and a phenylalanine‐derived alkyne synthesised by both Ohira–Bestmann and Corey–Fuchs‐based alkynylation protocols. Several members of this family of compounds showed promising anti‐trypanosomal activity. Unexpectedly, one of the most active compounds was allyl sulfone 24, which stems from the isomerisation of vinyl sulfone 5, and is presumably a reversible inhibitor. A docking study of the analogues in the active site of the parasitic cysteine protease rhodesain was carried out in order to gain an insight into their likely interactions with these enzymes.

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Reversible Radical Addition Guides Selective Photocatalytic Intermolecular Thiol‐Yne‐Ene Molecular Assembly

Shlapakov,

Kobelev,

Burykina

et al. 2024

Angewandte Chemie

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In the realm of modern organic chemistry, harnessing the power of multicomponent radical reactions presents both significant challenges and extraordinary potential. This article delves into this scientific frontier by addressing the critical issue of controlling selectivity in such complex processes. We introduce a novel approach that revolves around the reversible addition of thiyl radicals to multiple bonds, reshaping the landscape of multicomponent radical reactions. The key to selectivity lies in the intricate interplay between reversibility and the energy landscapes governing C‐C bond formation in thiol‐yne‐ene reactions. The developed approach not only allows to prioritize the thiol‐yne‐ene cascade, dominating over alternative reactions, but also extends the scope of coupling products obtained from alkenes and alkynes of various structures and electron density distributions, regardless of their relative polarity difference, opening doors to more versatile synthetic possibilities. In the present study, we provide a powerful tool for atom‐economical C‐S and C‐C bond formation, paving the way for the efficient synthesis of complex molecules. Carrying out our experimental and computational studies, we elucidated the fundamental mechanisms underlying radical cascades, a knowledge that can be broadly applied in the field of organic chemistry.

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Aminooxylation Horner–Wadsworth–Emmons Sequence for the Synthesis of Enantioenriched γ-Functionalized Vinyl Sulfones

Cited by 21 publications

References 83 publications

Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides

Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides

Synthesis and Evaluation of 1,2,3‐Triazole‐Containing Vinyl and Allyl Sulfones as Anti‐Trypanosomal Agents

Reversible Radical Addition Guides Selective Photocatalytic Intermolecular Thiol‐Yne‐Ene Molecular Assembly

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