α,β‐Unsaturated Acyl Cyanides as New Bis‐Electrophiles for Enantioselective Organocatalyzed Formal [3+3]Spiroannulation

Goudedranche, Sébastien; Bugaut, Xavier; Constantieux, Thierry; Bonne, Damien; Rodríguez, Jean

doi:10.1002/chem.201303613

Cited by 55 publications

(26 citation statements)

References 93 publications

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“…( E )‐Cinnamoyl Cyanide (6a): Compound 6a was prepared in an analogous way to compound 6b , using cinnamoyl chloride (12.173 g, 73.1 mmol) and crystallized from toluene to yield a white solid (10.251 g, 89 %). Mp 115–117 °C (lit.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Dicarbonyl Curcumin Analogues Containing the Tropane Scaffold

et al. 2019

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A general synthetic route to the unknown 1,3‐dicarbonyl tropane derived curcumin analogues was developed. The method was based on the aldol condensation reaction (40–90 % yield, two steps without product isolation) and acylation of the resulting 2‐benzylidenetropinones with substituted cinnamoyl cyanides (yields 41–91 %). Overall 18 new tropane derivatives featuring the characteristic curcuminoid hepta‐1,6‐dien‐3,5‐dione structure were synthesized and characterized. The range of the substituted aromatic rings in the prepared analogues included Ph, m‐MeO‐C6H4, 3,4‐di‐MeO‐C6H3, 3,4,5‐tri‐MeO‐C6H2, p‐Br‐C6H4, p‐F‐C6H4, p‐CF3‐C6H4, p‐NO2‐C6H4, 2‐NO2‐4,5‐di‐CH3O‐C6H2, 2‐NO2‐4,5‐O‐CH2‐O‐C6H2, 3‐MeO‐4‐[CH(CH3)‐OEt]‐C6H3, 3‐MeO‐4‐OH‐C6H3, p‐MeO‐C6H4, 4,5‐O‐CH2‐O‐C6H3, 3‐MeO‐4‐MeOCOO. Two orthogonal protective groups for hydroxyl (acetal or carbonate), removable in acidic or basic conditions, were used for synthesizing curcuminoids with free phenolic groups (3‐MeO‐4‐OH‐C6H3).

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Section: Methodsmentioning

confidence: 99%

Synthesis of Dicarbonyl Curcumin Analogues Containing the Tropane Scaffold

et al. 2019

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“…The first challenge of our study was to identify acyclic methylene β‐ketoamide substrates that could combine both good reactivity and selectivity. Our former studies of the organocatalytic Michael addition of cyclic α‐substituted β‐ketoamides to α,β‐unsaturated carbonyl compounds7d, 8a, d–e or nitroolefins6g highlighted the importance of the presence of a proton on the nitrogen atom. Its absence generally resulted in no reactivity and the acidity of the secondary amide could be correlated with the observed enantioselectivities.…”

Section: Resultsmentioning

confidence: 99%

Organocatalytic Enantio‐ and Diastereoselective Conjugate Addition to Nitroolefins: When β‐Ketoamides Surpass β‐Ketoesters

Rodríguez

Bugaut

et al. 2014

Chemistry A European J

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Our findings on the bifunctional squaramide-catalyzed enantioselective conjugate addition of β-ketoamides to nitroolefins are disclosed. It appears that simple acyclic methylene β-ketoamides, unlike the extensively studied β-ketoesters, afford the products in excellent diastereoselectivities, and maintain high yields and enantioselectivities. Moreover, competition and kinetic studies were conducted to rationalize the observed reactivity and selectivity. The high level of diastereocontrol, along with the amenability of the amide group to postfunctionalization, dramatically increase the synthetic usefulness of the transformation.

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“…In 2012, Wang and co-workers used organocatalytic inverse-electron-demand Diels-Alder reactions to efficiently construct spiro-piperidine skeletons [41]. In addition, Rodriguez and co-workers developed a different approach for asymmetric synthesis of spiro-piperidines, in which α-branched β-ketoamide-based [3 + 3] cycloaddition is catalyzed by bifunctional thiourea-tertiary amine [42]. Despite these advances, As part of our ongoing research program on organocatalytic synthesis of various drug-like spirocyclic scaffolds [44][45][46][47], we wondered whether we could synthesize chiral spirocyclic piperidones via asymmetric catalysis if we adjusted the sequence of reaction steps in this one-pot stepwise reaction.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Two-Step Organocatalytic Asymmetric Synthesis of Spirocyclic Piperidones via Wolff Rearrangement–Amidation–Michael–Hemiaminalization Sequence

et al. 2017

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A highly enantioselective organocatalytic Wolff rearrangement-amidation-Michaelhemiaminalization stepwise reaction is described involving a cyclic 2-diazo-1,3-diketone, primary amine and α,β-unsaturated aldehyde. Product stereocontrol can be achieved by adjusting the sequence of steps in this one-pot multicomponent reaction. This approach was used to synthesize various optically active spirocyclic piperidones with three stereogenic centers and multiple functional groups in good yields up to 76%, moderate diastereoselectivities of up to 80:20 and high enantioselectivities up to 97%.

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α,β‐Unsaturated Acyl Cyanides as New Bis‐Electrophiles for Enantioselective Organocatalyzed Formal [3+3]Spiroannulation

Cited by 55 publications

References 93 publications

Synthesis of Dicarbonyl Curcumin Analogues Containing the Tropane Scaffold

Synthesis of Dicarbonyl Curcumin Analogues Containing the Tropane Scaffold

Organocatalytic Enantio‐ and Diastereoselective Conjugate Addition to Nitroolefins: When β‐Ketoamides Surpass β‐Ketoesters

One-Pot Two-Step Organocatalytic Asymmetric Synthesis of Spirocyclic Piperidones via Wolff Rearrangement–Amidation–Michael–Hemiaminalization Sequence

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