Chalcogenide–Lewis Acid Mediated Tandem Michael Aldol Reaction — an Alternative to the Morita–Baylis–Hillman Reaction and a New Development

Kataoka, Tadashi; Kinoshita, Hironori

doi:10.1002/ejoc.200400610

Cited by 82 publications

(9 citation statements)

References 100 publications

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“…The catalytic role of enol ethers for the isomerization of 1 to II is reminiscent of the role that amines and phosphines play in the Baylis-Hillman reaction; [18] these Lewis bases promote a kind of aldol addition of unsaturated carbonyl compounds to aldehydes to provide the same unsaturated carbonyl compounds, the H on the Ca being replaced with 1-hydroxyalkyl groups. Accordingly, we examined a variety of Lewis bases in order to isolate or detect the intermediate II, or to accelerate the present [4+2] cycloaddition reaction.…”

Section: Resultsmentioning

confidence: 99%

Chameleon Reactivity of the Allene Bond of 4‐Vinylidene‐2‐oxazolidinone: Novel Through‐Space Conjugative Nucleophilic Addition of Electron‐Rich Alkenes and Hetero‐Nucleophiles

Kimura

Horino

Mori

et al. 2007

Chemistry A European J

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The Calpha==Cbeta double bond of allene carbamates 1 serves as an electron acceptor similar to the double bond of conjugated enones by means of a through-space interaction with the N--SO2 bond; the carbamate double bond is thus subject to nucleophilic addition for a wide variety of nucleophiles, which proceeds under mild conditions by heating at 70-100 degrees C. Depending on the kind of nucleophiles, 1 displays three different reaction modes: 1) Typically enol ethers and allylsilanes promote 1,3-sulfonyl migration of 1 and undergo the inverse electron demand Diels-Alder reaction with the 1-aza-1,3-butadiene intermediates II thus formed to furnish bicyclic 2-alkoxy-5-sulfonyltetrahydropyridines 2 and 2-silylmethyl-5-sulfonyltetrahydropyridines 3, respectively, with high regio- and stereoselectivity and retention of configuration of the double bonds of these electron-rich alkenes; 2) silanes (RnSiH4-n, n=1-3) and thiols deliver the hydride and the thiolate at the Cbeta carbon and promote the 1,3-sulfonyl migration, followed by protonation of the thus-formed carbamate anion (Z)-III to provide, for example, (Z)-4 a and (Z)-4 j, respectively; 3) alcohols simply add to the Calpha==Cbeta double bond and provide (E)-6. Usually, the reaction with alcohols is accompanied by the second pathway, giving rise to, for example, (Z)-4 b in addition to (E)-6 b. Phenol engages in the third pathway and provides (E)-6 g exclusively. Heteroaromatics, such as furans and benzofurans follow the first pathway, however, in a different regioselectivity from enol ethers and allylsilanes, delivering the oxygen atom at the 3-position of 5-sulfonyltetrahydropyridines (2 g and 2 h). Indoles, on the other hand, show a dichotomy, equally enjoying the first and the third pathways and provide mixtures of (E)-7 and (E)-8, respectively.

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Section: Resultsmentioning

confidence: 99%

Chameleon Reactivity of the Allene Bond of 4‐Vinylidene‐2‐oxazolidinone: Novel Through‐Space Conjugative Nucleophilic Addition of Electron‐Rich Alkenes and Hetero‐Nucleophiles

Kimura

Horino

Mori

et al. 2007

Chemistry A European J

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“…The metal-mediated domino Michael/aldol reaction of 1 to give 3 via the enolate 2 is the most widely utilized domino process (Scheme 8.1), whereby three stereogenic centers can be formed [3]. The reaction is an exceedingly reliable transformation, and allows for a great variety of reaction conditions [4].…”

Section: Metal-mediated Domino Michael/aldol Reactionsmentioning

confidence: 99%

Domino Reactions Involving Catalytic Enantioselective Conjugate Additions

Tietze

Düfert

2010

Catalytic Asymmetric Conjugate Reactions

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“…The disadvantages of this reaction are slow reaction rate and long reaction time. It is often reported that a few days or a few weeks have been required for the reaction to be completed [5][6][7][8].…”

Section: Introductionmentioning

confidence: 98%

l-proline and l-histidine co-catalyzed Baylis–Hillman reaction

2011

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Baylis-Hillman reaction between an aldehyde and an activated alkene, such as alkyl vinyl ketones, acrylates, acrylonitrile, and vinylsulfones, giving the b-hydroxy-a-methylene carbonyl compounds, is a versatile and atom-economical carbon-carbon bond-forming reaction. This reaction usually is catalyzed by strong Lewis bases such as tertiary amines and suffers from slow reaction rate. In this paper the Baylis-Hillman reaction between arylaldehydes and methyl vinyl ketone was successfully realized by a catalytic amount of L-proline and L-histidine system to give the corresponding normal Baylis-Hillman adducts in moderate to high yields for the first time. The effects of solvent and reagent electro property on the yields of this reaction were also investigated. Proline and histidine are naturally widely present amino acids in food system; furthermore, aldehydes and activated alkenes can also be easily produced in food processing, so proline and histidine co-catalyzed Baylis-Hillman reaction may find application in explaining some phenomena in food processing.

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Chalcogenide–Lewis Acid Mediated Tandem Michael Aldol Reaction — an Alternative to the Morita–Baylis–Hillman Reaction and a New Development

Cited by 82 publications

References 100 publications

Chameleon Reactivity of the Allene Bond of 4‐Vinylidene‐2‐oxazolidinone: Novel Through‐Space Conjugative Nucleophilic Addition of Electron‐Rich Alkenes and Hetero‐Nucleophiles

Chameleon Reactivity of the Allene Bond of 4‐Vinylidene‐2‐oxazolidinone: Novel Through‐Space Conjugative Nucleophilic Addition of Electron‐Rich Alkenes and Hetero‐Nucleophiles

Domino Reactions Involving Catalytic Enantioselective Conjugate Additions

l-proline and l-histidine co-catalyzed Baylis–Hillman reaction

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