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Relevant academic research and scientific papers

P-Stereogenic β-Aminophosphines: Preparation and Applications in Enantioselective Organocatalysis

The synthesis of stereodefined β-aminophosphines having both carbon- and phosphorus-based chirality centers is described. The method involves resolution of a mixture of β-aminophosphine oxide diastereomers accessed by ring-opening of an amino alcohol-derived cyclic sulfamidate. A stereospecific, borane-promoted reduction of β-aminophosphine oxides, which occurs under mild conditions and with inversion of configuration at phosphorus, is a key step in this process. The products obtained are new building blocks for the synthesis of P-chiral ligands and organocatalysts. In a proof-of-concept application in organocatalysis, the diastereomeric P-chiral β-aminophosphine-based bifunctional thioureas displayed significantly different activities in the Morita-Baylis-Hillman reaction of methyl acrylate with benzaldehyde derivatives.

Asymmetric Morita–Baylis–Hillman Reaction: Catalyst Development and Mechanistic Insights Based on Mass Spectrometric Back-Reaction Screening

An efficient protocol for the evaluation of catalysts for the asymmetric Morita–Baylis–Hillman (MBH) reaction was developed. By mass spectrometric back-reaction screening of quasi-enantiomeric MBH products, an efficient bifunctional phosphine catalyst was identified that outperforms literature-known catalysts in the MBH reaction of methyl acrylate with aldehydes. The close match between the selectivities measured for the forward and back reaction and kinetic measurements provided strong evidence that the aldol step and not the subsequent proton transfer is rate- and enantioselectivity-determining.

Bifunctional (Thio)urea-Phosphine Organocatalysts Derived from d -Glucose and α-Amino Acids and Their Application to the Enantioselective Morita-Baylis-Hillman Reaction

Novel (thio)urea-tertiary phosphines were developed for use as bifunctional organocatalysts readily available from naturally occurring molecules: saccharides and amino acids. The efficiency of the organocatalysts was demonstrated in the asymmetric Morita-

Enantioselective Morita-Baylis-Hillman reaction promoted by l-threonine-derived phosphine-thiourea catalysts

A series of bifunctional phosphine-thiourea organic catalysts based on natural amino acid scaffolds were designed and prepared. l-Threonine-derived bifunctional phosphine catalysts were found to be very efficient in promoting asymmetric Morita-Baylis-Hillman (MBH) reaction of acrylates with aromatic aldehydes, affording the desired MBH adducts with up to 90% ee. To gain mechanistic insights into the reaction, the effects of adding various additives on the MBH reaction were investigated. We propose that the hydrogen bonding interactions between the thiourea moiety of the catalyst and the enolate intermediate are crucial for the stereochemical outcome of the reaction. The method described in this report may provide a practical solution to the enantioselective MBH reaction of simple acrylates.

A new dual catalytic system for asymmetric morita-baylis-hillman reaction

High yields and enantioselectivities up to 88% were achieved in asymmetric Morita-Baylis-Hillman reactions using a combination of chiral amino acid derived guanidines and triphenylphosphane as a novel dual catalytic system.