Imidazole-catalysed Baylis–Hillman reactions: a new route to allylic alcohols from aldehydes and cyclic enones

Gatri, Rafik; Gaïed, M. M. El

doi:10.1016/s0040-4039(02)01515-0

Cited by 85 publications

(30 citation statements)

References 11 publications

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“…Comparable or slightly lower yields to those reported [7,8,9,10] were observed in the case of the reaction of cyclohexenone with formaldehyde (i.e., 3). However, the reaction rate increase was quite significant with the SDS reaction being complete in under 1 hour (65%) as compared to multiple hours or more commonly days for known literature procedures.…”

Section: Resultsmentioning

confidence: 42%

“…Initial efforts concentrated on two protocols [that is, 1) DMAP/60 8C/5 days/68% and 2) imidazole/room temperature/17 days/93%] reported by El Gaïed, [7,8] for the conversion of 5,5-dimethylcyclohexenone to the corresponding MBH product. However, translation (and modification) of these conditions to substrate 6 gave at best yields of 4 in the range of 30%.…”

Section: Resultsmentioning

confidence: 99%

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Cyclic Enones as Substrates in the Morita–Baylis–Hillman Reaction: Surfactant Interactions, Scope and Scalability with an Emphasis on Formaldehyde

et al. 2009

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Traditionally, cyclic enones and formalin are reactants notorious for displaying problematic behaviour (i.e., poor solubility and low yields) under Morita-Baylis-Hillman (MBH) reaction conditions. The body of research presented herein focuses on the use of surfactants in water as a solvent medium that offers a resolution to many of the issues associated with the MBH reaction. Reaction scope, scalability and small angle X-ray scattering have been studied to assist with the understanding of the reaction mechanism and industrial application. A comparison against known literature methods for reaction scale-up is also discussed.

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Section: Resultsmentioning

confidence: 42%

Section: Resultsmentioning

confidence: 99%

Cyclic Enones as Substrates in the Morita–Baylis–Hillman Reaction: Surfactant Interactions, Scope and Scalability with an Emphasis on Formaldehyde

et al. 2009

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“…The starting materials 1a and 1b were prepared in a two‐step sequence according to previous reports. Indeed, allylic alcohols 2a and 2b were first prepared through the MBH reaction involving the cyclohex‐2‐enone , followed by their direct conversion into the corresponding allylic bromides 1a and 1b using aqueous 48% HBr ( Scheme ) .…”

Section: Resultsmentioning

confidence: 99%

A Metal‐Free Synthesis of 2‐Alkyl(or Aryl) Thiomethyl‐2‐cyclohexenones from Cyclic Morita–Baylis–Hillman Bromides

Baioui

Abidi

Rezgui

2016

Helvetica Chimica Acta

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Under mild conditions, an efficient and rapid S‐allylation of thiols with cyclic Morita–Baylis–Hillman (MBH) bromides without the need of a transition‐metal catalyst or an expensive additive is described herein. Treatment of the MBH bromides with various thiols or ethane‐1,2‐dithiol in the presence of Et3N regioselectively affords the corresponding 2‐alkyl(or aryl) thiomethyl‐2‐cyclohexenones or the perhydro benzo[1,4]dithiepinone, respectively, in moderate to good yields (40 – 73%). The reaction is rapid and carried out in THF at room temperature.

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“…Among them, imidazole was found to catalyze BaylisHillman reactions of cyclopent-2-enone with various aldehydes in stoichiometric amounts in neutral aqueous media [9]. Later, rate acceleration of both imidazoleand other azole-promoted Baylis-Hillman reactions was reported in sodium hydrogen carbonate solution [10,11].…”

Section: Introductionmentioning

confidence: 99%

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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Imidazole-catalysed Baylis–Hillman reactions: a new route to allylic alcohols from aldehydes and cyclic enones

Cited by 85 publications

References 11 publications

Cyclic Enones as Substrates in the Morita–Baylis–Hillman Reaction: Surfactant Interactions, Scope and Scalability with an Emphasis on Formaldehyde

Cyclic Enones as Substrates in the Morita–Baylis–Hillman Reaction: Surfactant Interactions, Scope and Scalability with an Emphasis on Formaldehyde

A Metal‐Free Synthesis of 2‐Alkyl(or Aryl) Thiomethyl‐2‐cyclohexenones from Cyclic Morita–Baylis–Hillman Bromides

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

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