345358-57-8

Upstream product

• 345358-13-6 (S)-3-phenyl-3-(1-methyl-1H-pyrrol-2-yl)-propanal 
• 96-54-8 N-Methylpyrrole 
• 104-55-2 3-phenyl-propenal 
• 14371-10-9 (E)-3-phenylpropenal 

Downstream Products

• 112607-26-8 (S)-α-Phenyl-γ-butyrolactone 
• 6837-05-4 (2S)-2-phenylbutane-1,4-diol 

Relevant academic research and scientific papers

Chiral GAP catalysts of phosphonylated imidazolidinones and their applications in asymmetric Diels-Alder and Friedel-Crafts reactions

The design and synthesis of recyclable imidazolidinone catalysts using GAP chemistry/technique was described. Their applications in asymmetric Diels-Alder and Friedel-Crafts reactions with α,β-unsaturated aldehydes resulted in excellent yields and higher enantioselectivities than previous processes. As recyclable small molecular catalysts, phosphonylated imidazolidinones can be recovered and reused for up to three runs without costing significant decrease in catalytic activity.

Improving catalyst activity in secondary amine catalysed transformations

The effect on catalyst performance of altering substituents at the 2-position of the Macmillan imidazolidinone has been examined. Condensation of l-phenylalanine N-methyl amide with acetophenone derivatives results in a series of imidazolidinones whose sa

Aromatic Interactions in Organocatalyst Design: Augmenting Selectivity Reversal in Iminium Ion Activation

Substituting N-methylpyrrole for N-methyindole in secondary-amine-catalysed Friedel-Crafts reactions leads to a curious erosion of enantioselectivity. In extreme cases, this substrate dependence can lead to an inversion in the sense of enantioinduction. Indeed, these closely similar transformations require two structurally distinct catalysts to obtain comparable selectivities. Herein a focussed molecular editing study is disclosed to illuminate the structural features responsible for this disparity, and thus identify lead catalyst structures to further exploit this selectivity reversal. Key to effective catalyst re-engineering was delineating the non-covalent interactions that manifest themselves in conformation. Herein we disclose preliminary validation that intermolecular aromatic (CH-π and cation-π) interactions between the incipient iminium cation and the indole ring system is key to rationalising selectivity reversal. This is absent in the N-methylpyrrole alkylation, thus forming the basis of two competing enantio-induction pathways. A simple L-valine catalyst has been developed that significantly augments this interaction.

Infrared multiphoton dissociation spectroscopic analysis of noncovalent interactions in organocatalysis

Herein we report the first application of infrared multiple-photon dissociation (IRMPD) spectroscopy to study noncovalent interactions in organocatalysis. Phenylalanine-derived iminium ions, central to numerous organocatalytic processes, display dynamic conformational behavior as a consequence of stabilizing noncovalent interactions (e.g., CH-π, π-π). Electronic modulation of the aryl ring causes notable variation in the conformation; this can be detected spectroscopically and correlated with enantioselectivity. Given that these interactions, which orchestrate stereoinduction, encode for specific conformers (I, II, or III), a diagnostic IRMPD spectrum is generated: the C=O stretching frequency of the imidazole carbonyl group serves as a diagnostic marker. The calculated conformers and their respective spectra can be compared with experimental data. Consequently, valuable insight into the ubiquitous noncovalent interactions associated with MacMillan-catalyst-derived α,β-unsaturated iminium ions can be obtained in the absence of solvent or counterion effects. A preliminary structure-catalysis correlation is disclosed, thus demonstrating the potential of this approach for studying reactive intermediates and facilitating catalyst design.

A chiral organocatalytic polymer-based monolithic reactor

Radical copolymerisation of divinylbenzene and a properly modified enantiomerically pure imidazolidinone inside a stainless steel column in the presence of dodecanol and toluene as porogens afforded the first example of a chiral organocatalyst immobilized

Noncovalent interactions in organocatalysis: Modulating conformational diversity and reactivity in the MacMillan catalyst

Intriguing imidazolidinones! Inspired by noncovalent interactions in proteins, a series of electronically distinct MacMillan catalysts were designed. The effect of electronic modulation on ground state conformation, reactivity, and performance was studied in a catalytic setting with intriguing outcomes. Copyright

Fluoro-organocatalysts: Conformer equivalents as a tool for mechanistic studies

Fluorine in charge! The fluorine-iminium ion gauche effect has been exploited in the design of conformational probes for organocatalysis (see scheme). Stabilizing hyperconjugative [σC H→σ *C F] and/or electrostatic [N+ Fσ-] interactions render the C F bond an excellent steering group for controlling molecular topology without introducing additional steric constraints.

Imidazolethiones: novel and efficient organocatalysts for asymmetric Friedel-Crafts alkylation

Imidazolethiones organocatalyzed the asymmetric Friedel-Crafts alkylation of pyrroles with α,β-unsaturated aldehydes was achieved to afford the corresponding adducts in moderate to good yields and good to excellent enantioselectivities. The possible mecha

HETEROGENEOUS CHIRAL CATALYST

The invention provides a heterogeneous catalyst comprising a catalytic group coupled to a mesocellular siliceous foam support. The catalytic group is capable of catalysing a reaction selected from the group consisting of a Friedel-Craft reaction and a Die