A General Asymmetric Formal Synthesis of Aza‐Baylis–Hillman Type Products under Bifunctional Catalysis

Frías, María A.; Carrasco, Ana C.; Fraile, Alberto; Alemán, José V.

doi:10.1002/chem.201705218

Cited by 24 publications

(12 citation statements)

References 47 publications

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“…The good performance of the reaction was also due to the ad hoc-placed R 2 -R 4 substituents of the dienal starters 129 ; almost all successful examples concerned γ-phenyl-substituted hexadienals (R 2 = Ph), while the use of unsubstituted 2,4-hexadienal or 2,4-heptadienal gave aza-Baylis–Hillman-type products (not shown). 109 The authors referred to the overall reaction as a normal-electron-demand aza-Diels–Alder reaction, and they did not enter into details about either the concerted or Mannich-initiated stepwise nature of the mechanism.…”

Section: Vinylogous Aldehydesmentioning

confidence: 99%

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

et al. 2020

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The principle of vinylogy states that the electronic effects of a functional group in a molecule are possibly transmitted to a distal position through interposed conjugated multiple bonds. As an emblematic case, the nucleophilic character of a π-extended enolate-type chain system may be relayed from the legitimate α-site to the vinylogous γ, ε, ..., ω remote carbon sites along the chain, provided that suitable HOMO-raising strategies are adopted to transform the unsaturated pronucleophilic precursors into the reactive polyenolate species. On the other hand, when “unnatural” carbonyl ipso -sites are activated as nucleophiles (umpolung), vinylogation extends the nucleophilic character to “unnatural” β, δ, ... remote sites. Merging the principle of vinylogy with activation modalities and concepts such as iminium ion/enamine organocatalysis, NHC-organocatalysis, cooperative organo/metal catalysis, bifunctional organocatalysis, dicyanoalkylidene activation, and organocascade reactions represents an impressive step forward for all vinylogous transformations. This review article celebrates this evolutionary progress, by collecting, comparing, and critically describing the achievements made over the nine year period 2010–2018, in the generation of vinylogous enolate-type donor substrates and their use in chemical synthesis.

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Section: Vinylogous Aldehydesmentioning

confidence: 99%

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

et al. 2020

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“…Solvents were dried with standard methods and freshly distilled prior to use if needed. 3-(2-Pyridyl)benzoic acids 1 , 1,3-bis(2-pyridyl)benzene 5 , bis(imidazoline)benzene 7 , , and the sulfonimines 10 and 12 were prepared according to the literature methods. All other chemicals were used as purchased.…”

Section: Methodsmentioning

confidence: 99%

Chiral (Pyridine)-(Imidazoline) NCN′ Pincer Palladium(II) Complexes: Convenient Synthesis via C–H Activation and Characterization

et al. 2022

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A series of aryl-based chiral NCN′ pincer palladium-(II) complexes 4a−k were synthesized via C−H activation of the (pyridyl)-(imidazolinyl)benzene ligands, which proceeded smoothly with PdCl 2 as the palladium source in the presence of Et 3 N or NaHCO 3 base in toluene under reflux. All of the complexes have been characterized by elemental analysis and 1 H and 13 C{ 1 H} NMR spectroscopy. In addition, the molecular structures of complexes 4a, 4c, and 4f have been determined by X-ray singlecrystal diffraction analysis. The obtained chiral Pd pincers were applied to catalytic asymmetric reactions of acrylonitrile and dichloroacetonitrile with sulfonimines. With a catalyst loading of 5 mol % and the assistance of AgOAc, these complexes acted as active but moderately stereoselective catalysts for the aforementioned reactions.

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“…[78] We have provided ag eneral method for the synthesis of aw ide range of aza-Baylis-Hillman-type products with excellent enantioselectivities, which are difficult to obtain by other methodologies. [78] We have provided ag eneral method for the synthesis of aw ide range of aza-Baylis-Hillman-type products with excellent enantioselectivities, which are difficult to obtain by other methodologies.…”

Section: Bifunctional Organocatalytic Cinchona Derivativesmentioning

confidence: 99%

Development and Application of Asymmetric Organocatalytic Mukaiyama and Vinylogous Mukaiyama‐Type Reactions

Frías

Cieślik

Fraile

et al. 2018

Chemistry A European J

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Organocatalysis is a growing area that is benefiting from advances in many fields. Its implementation has begun in areas such as supramolecular chemistry, organic chemistry and natural product synthesis. While a considerable number of important publications in the field of organocatalytic Mukaiyama-type additions have been reported, they are yet to be fully covered in a review. Therefore, we would like to highlight the applications of various kinds of organocatalysts in Mukaiyama-type reactions, while also including the vinylogous Mukaiyama variation. Herein we describe and discuss the development and current state of the art of the organocatalytic Mukaiyama reaction, vinylogous Mukaiyama and related reactions.

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A General Asymmetric Formal Synthesis of Aza‐Baylis–Hillman Type Products under Bifunctional Catalysis

Cited by 24 publications

References 47 publications

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

Chiral (Pyridine)-(Imidazoline) NCN′ Pincer Palladium(II) Complexes: Convenient Synthesis via C–H Activation and Characterization

Development and Application of Asymmetric Organocatalytic Mukaiyama and Vinylogous Mukaiyama‐Type Reactions

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