137480-06-9

Upstream product

• 591-87-7 Allyl acetate 
• 102619-05-6 1-(toluene-4-sulfonyl)-1H-pyrrole-2-carbaldehyde 
• 3052-45-7 allyllithium 

Downstream Products

• 137567-19-2 (R)-1-(N-tosylpyrrol-2-yl)but-3-en-1-ol 

Relevant academic research and scientific papers

Catalytic, nucleophilic allylation of aldehydes with allyl acetate

(Chemical Equation Presented) A new catalytic allylation of aldehydes has been developed that employs allyl acetate as the allylating reagent. Under catalysis by ruthenium trichloride (3 mol %) in the presence of carbon monoxide (30 psi), water (1.5 equiv), and Methylamine (0.1 equiv), a wide range of aromatic, olefinic, and aliphatic aldehydes are efficiently allylated under mild conditions (70 °C, 24-48 h). The stoichiometric byproducts of this reaction are carbon dioxide and acetic acid.

Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction

The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.

METHOD FOR FORMING ALLYLIC ALCOHOLS

A method of performing a chemical reaction includes reacting an allyl donor and a substrate in a reaction mixture, and forming a homoallylic alcohol in the reaction mixture. The substrate may be an aldehyde or a hemiacetal. The reaction mixture includes a ruthenium catalyst, carbon monoxide at a level of at least 1 equivalent relative to the substrate, and water at a level of at least 1 equivalent relative to the substrate, and an amine at a level of from 0 to 0.5 equivalent relative to the substrate. The reaction mixture may also include a halide, and the equivalents of the amine may be similar to those of the halide. The reacting includes maintaining the reaction mixture at a temperature of at least 40°C. The method may be catalytic in metal, environmentally benign, amenable to large-scale applications, and applicable to a wide range of substrates.

Preparation of Optically Active Pyrrol-2-ylmethanols by Kinetic Resolution Using the Modified Sharpless Asymmetric Epoxidation Reagent

Kinetic resolution of pyrrol-2-ylmethanols was carried out by using the modified Sharpless asymmetric epoxidation reagent to give the slow-reaction enantiomers (R)-3a-g and (S)-3b,d with high enantioselectivity (>90percent e.e.) and high chemical yield (30 - 43percent)