1238053-85-4

Upstream product

• 459-57-4 4-fluorobenzaldehyde 
• 292638-85-8 acrylic acid methyl ester 
• 1132641-31-6 methyl 2-(((tertbutoxycarbonyl)oxy)(4-fluorophenyl)methyl)acrylate 

Relevant academic research and scientific papers

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-

Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments.

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.

Organocatalytic peroxy-asymmetric allylic alkylation

The peroxy-asymmetric allylic alkylation of hydroperoxyalkanes with Morita-Baylis-Hillman carbonates was catalysed by modified cinchona alkaloids (up to 93% ee), from which chiral α-methylene-β-hydroxy esters could be efficiently derived.