The Use of Sulfonyl 1,3-Dienes in Organic Synthesis

Bäckvall, Jan‐E.; Chinchílla, Rafael; Nájera, Carmén; Yus, Miguel

doi:10.1021/cr970326z

Cited by 144 publications

(52 citation statements)

References 127 publications

(280 reference statements)

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“…The molecular structure of 7 was confirmed by X-ray analysis. [15] This sequential reaction provides a conceptually new type of [3+3]cycloaddition system between propargylic alcohols and alkenes. [16] In summary, the ruthenium-catalyzed 6-endo-cycloisomerization of 1,5-enynes gave the corresponding 1,3-cyclohexadienes in high to excellent yields.…”

Section: Methodsmentioning

confidence: 99%

Catalytic Cycloisomerization of 1,5‐Enynes to 1,3‐Cyclohexadienes via Ruthenium Vinylidene Intermediates

2009

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Another way to dienes: The ruthenium-catalyzed 6-endo-cycloisomerization of 1,5-enynes gives the corresponding 1,3-cyclohexadienes in high to excellent yields. This novel synthetic and catalytic method constitutes another way to selectively prepare 1,3-cyclohexadienes, this cyclic diene skeleton being a core subunit in many natural products and a useful building block for a variety of organic transformations.

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Section: Methodsmentioning

confidence: 99%

Catalytic Cycloisomerization of 1,5‐Enynes to 1,3‐Cyclohexadienes via Ruthenium Vinylidene Intermediates

2009

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“…As a synthetic route to yield 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes the Asscher–Vofsi reaction is usually applied . Another method leading to a broad variety of 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes is represented as the Michael addition of nucleophiles to 1‐arylsulfonyl 1,3‐dienes . Earlier, we have developed an alternative method for preparing 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes using arylation of conjugated dienes with aryl diazonium salts in the SO 2 saturated solution .…”

Section: Introductionmentioning

confidence: 99%

“…Earlier, we have developed an alternative method for preparing 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes using arylation of conjugated dienes with aryl diazonium salts in the SO 2 saturated solution . In contrast to the previously developed methods, this protocol is very simple, relatively fast, and does not need expensive reactants or catalysts …”

Section: Introductionmentioning

confidence: 99%

“…Although some of the presented reactions are not principally new, we propose synthetic procedures that are much faster, cheaper, and simpler than the previously developed synthesis. The described computational approach will be useful for studying chemical reactivity in the electrophile–nucleophile reactions of 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes, 1‐arylsulfonyl 1,3‐dienes, and the related compounds …”

Section: Introductionmentioning

confidence: 99%

“…In contrast to the mentioned butenes, the 2-arylsulfonyl 1,3-dienes, 1,3-bis(arylsulfonyl) 1,3-dienes and, especially, 2,3bis(arylsulfonyl) 1,3-diene compounds are studied much better. [14,15] In two recent exhaustive reviews, Flick and Padwa described a broad variety of syntheses towards azapolycyclic ring systems and piperidone derivatives. [16,17] One should note that the molecules containing the arylsulfonyl moiety are well known as physiologically active compounds, for example, sulfonamide drugs.…”

Section: Introductionmentioning

confidence: 99%

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A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine

Bondarchuk

Smalius

Minaev

2015

J. Phys. Org. Chem.

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Nucleophilic substitution and dehydrochlorination reactions of a number of the ring-substituted 1-(arylsulfonyl)-2-R-4-chloro-2-butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general rapidity, cheapness, and simplicity providing moderate to high yields of 1-arylsulfonyl 1,3-butadienes (48-95%), 1-(arylsulfonyl)-2-R-4-(N,N-dialkylamino)-2-butenes (31-53%), 1-(arylsulfonyl)-2-R-2-buten-4-ols (37-61%), and bis[4-(arylsulfonyl)-3-R-but-2-enyl]sulfides (40-70%). The density functional theory B3LYP/6-311++G(2d,2p) calculations of the intermediate allylic cations in acetone revealed their high stability occurring from a resonance stabilization and hyperconjugation by the SO 2 Ar group. The reactivity parameters estimated at the bond critical points of the diene/allylic moiety display a high correlation (R 2 > 0.97) with the Hammett (σ p ) constants. 1-Arylsulfonyl 1,3-butadienes are characterized by a partly broken π conjugated system, which follows from analysis of the two-centered delocalization (δ) and localization (λ) index values. The highest occupied molecular orbital energies of 1-arylsulfonyl 1,3-butadienes are lower than those of 1,3-butadiene explaining their low reactivity towards the Diels-Alder condensation.

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Desulfonylation Reactions

Alonso

Ájera

2009

Organic Reactions

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The use of sulfones in organic chemistry, acting as an auxiliary group, is still a very important synthetic strategy, especially for the formation of carbon‐carbon single and double bonds. Once the synthetic objective is achieved, the sulfone gruop is usually removed from the molecule. This removal most commonly involves a reductive desulfonylation process with either replacement of the sulfone by hydrogen, or a process that results in the formation of a carbon‐carbon double bond when a β‐hydroxy or β‐alkoxy sulfone is employed. This chapter is devoted to the replacement of the sulfone group by a hydrogen (reductive desulfonylation reactions), and reductive elimination reactions of Julia‐type substrates (Julia‐Lythgoe olefination process). The chapter addresses the full scope, generality, limitations, and synthetic applications of these reactions. The literature through most of 2007 is covered.

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The Use of Sulfonyl 1,3-Dienes in Organic Synthesis

Cited by 144 publications

References 127 publications

Catalytic Cycloisomerization of 1,5‐Enynes to 1,3‐Cyclohexadienes via Ruthenium Vinylidene Intermediates

Catalytic Cycloisomerization of 1,5‐Enynes to 1,3‐Cyclohexadienes via Ruthenium Vinylidene Intermediates

A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine

Desulfonylation Reactions

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