45966-73-2

Upstream product

• 4654-39-1 4-bromophenethanol 
• 79-10-7 acrylic acid 
• 10431-61-5 p-divinylbenzene monoepoxide 

Downstream Products

• 864846-94-6 3-(4-(2-hydroxyethyl)phenyl)propanenitrile 

Relevant academic research and scientific papers

Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control

Reversible catalytic reactions operate under thermodynamic control, and thus, establishing a selective catalytic system poses a considerable challenge. Herein, we report a reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting the lower barrier for C-CN oxidative addition and reductive elimination at benzylic positions in the absence of a cocatalytic Lewis acid. Through the design of a novel type of HCN donor, a practical, branched-selective, HCN-free transfer hydrocyanation was realized. The synthetically useful resolution of a mixture of branched and linear nitrile isomers was also demonstrated to underline the value of reversible and selective transfer reactions. In a broader context, this work demonstrates that high kinetic selectivity can be achieved in reversible transfer reactions, thus opening new horizons for their synthetic applications.

Regiodivergent Reductive Opening of Epoxides by Catalytic Hydrogenation Promoted by a (Cyclopentadienone)iron Complex

The reductive opening of epoxides represents an attractive method for the synthesis of alcohols, but its potential application is limited by the use of stoichiometric amounts of metal hydride reducing agents (e.g., LiAlH4). For this reason, the corresponding homogeneous catalytic version with H2 is receiving increasing attention. However, investigation of this alternative has just begun, and several issues are still present, such as the use of noble metals/expensive ligands, high catalytic loading, and poor regioselectivity. Herein, we describe the use of a cheap and easy-To-handle (cyclopentadienone)iron complex (1a), previously developed by some of us, as a precatalyst for the reductive opening of epoxides with H2. While aryl epoxides smoothly reacted to afford linear alcohols, aliphatic epoxides turned out to be particularly challenging, requiring the presence of a Lewis acid cocatalyst. Remarkably, we found that it is possible to steer the regioselectivity with a careful choice of Lewis acid. A series of deuterium labeling and computational studies were run to investigate the reaction mechanism, which seems to involve more than a single pathway.

Pd-Catalyzed Synthesis of Vinyl Arenes from Aryl Halides and Acrylic Acid

Acrylic acid is presented as an inexpensive, non-volatile vinylating agent in a palladium-catalyzed decarboxylative vinylation of aryl halides. The reaction proceeds through a Heck reaction of acrylic acid, immediately followed by protodecarboxylation of the cinnamic acid intermediate. The use of the carboxylate group as a deciduous directing group ensures high selectivity for monoarylated products. The vinylation process is generally applicable to diversely substituted substrates. Its utility is shown by the synthesis of drug-like molecules and the gram-scale preparation of key intermediates in drug synthesis.

Copper-mediated radical 1,2-bis(trifluoromethylation) of alkenes with sodium trifluoromethanesulfinate

An efficient chemoselective 1,2-bis(trifluoromethylation) of alkenes with CF3SO2Na promoted by t-BuOOH/CuCl was developed. This protocol provided the first convenient preparation of 1,2-bis(trifluoromethylated) compounds by the vicinal difunctionalization of alkenes. The chemoselectivity of this reaction was accomplished by increasing the concentration of the CF3 radical.