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• 5153-67-3 nitrostyrene 
• 428442-20-0 3-[(4-methoxyphenyl)sulfanyl]-3-oxopropanoic acid 
• 102-96-5 (2-nitroethenyl)benzene 
• 1353143-26-6 4-methoxybenzyl 3-[(4-methoxyphenyl)sulfanyl]-3-oxopropanoate 

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• 71657-88-0 (4R)-4-phenyl-2-pyrrolidone 

Relevant academic research and scientific papers

Anion-π Catalysis on Fullerenes

Anion-π interactions on fullerenes are about as poorly explored as the use of fullerenes in catalysis. However, strong exchange-correlation contributions and the localized π holes on their surface promise unique selectivities. To elaborate on this promise, tertiary amines are attached nearby. Dependent on their positioning, the resulting stabilization of anionic transition states on fullerenes is shown to accelerate disfavored enolate addition and exo Diels-Alder reactions enantioselectively. The found selectivities are consistent with computational simulations, particularly concerning the discrimination of differently planarized and charge-delocalized enolate tautomers by anion-π interactions. Enolate-π interactions on fullerenes are much shorter than standard π- π interactions and anion-π interactions on planar surfaces, and alternative cation-π interactions are not observed. These findings open new perspectives with regard to anion-π interactions in general and the use of carbon allotropes in catalysis.

Anion-π Catalysts with Axial Chirality

The idea of anion-π catalysis is to stabilize anionic transition states by anion-π interactions on aromatic surfaces. For asymmetric anion-π catalysis, π-acidic surfaces have been surrounded with stereogenic centers. This manuscript introduces the first anion-π catalysts that operate with axial chirality. Bifunctional catalysts with tertiary amine bases next to π-acidic naphthalenediimide planes are equipped with a bulky aromatic substituent in the imide position to produce separable atropisomers. The addition of malonic acid half thioesters to enolate acceptors is used for evaluation. In the presence of a chiral axis, the selective acceleration of the disfavored but relevant enolate addition was much better than with point chirality, and enantioselectivity could be observed for the first time for this reaction with small-molecule anion-π catalysts. Enantioselectivity increased with the π acidity of the π surface, whereas the addition of stereogenic centers around the aromatic plane did not cause further improvements. These results identify axial chirality of the active aromatic plane generated by atropisomerism as an attractive strategy for asymmetric anion-π catalysis.

Mono thiomalonates as thioester enolate equivalents - Enantioselective 1,4-addition reactions to nitroolefins under mild conditions

Mono thiomalonates (MTMs) are introduced as thioester enolate equivalents. Asymmetric organocatalyzed conjugate addition reactions to nitroolefins proceed under mild conditions to afford synthetically useful γ-nitrothioesters with excellent yields and ena

Organocatalytic Enantioselective Michael-Addition of Malonic Acid Half-Thioesters to β-Nitroolefins: From Mimicry of Polyketide Synthases to Scalable Synthesis of γ-Amino Acids

Highly enantioselective biomimetic Michael addition reactions of malonic acid half thioesters (MAHTs) to a variety of nitroolefins, affording the optically active γ-amino acid precursors, were developed by employing the Cinchona-based squaramides (up to >

Mimicry of polyketide synthases - Enantioselective 1,4-addition reactions of malonic acid half-thioesters to nitroolefins

Bifunctionality is the key for mimicking the active site of polyketide synthases with synthetic metal-free organocatalysts (see picture). Cinchona alkaloid derivatives bearing both a basic site and a urea moiety catalyze conjugate enantioselective addition reactions of malonic acid half thioesters (MAHTs) to nitroolefins with up to quantitative yields and selectivities up to 90% ee. (Chemical Equation Presented).