1179358-90-7

Upstream product

• 99802-91-2 2-cinnamoyl-1-methyl-1H-imidazole 
• 616-47-7 1-methyl-1H-imidazole 
• 2021-28-5 ethyl dihydrocinnamate 
• 1179358-94-1 (E)-1-(1-methyl-1H-imidazol-2-yl)-3-phenylprop-2-en-1-ol 

Downstream Products

• 103-25-3 3-phenylpropanoic acid methyl ester 

Relevant academic research and scientific papers

Light-Driven Enantioselective Synthesis of Pyrroline Derivatives by a Radical/Polar Cascade Reaction

Herein, a light-driven, atom-economical process that provides access to enantiomerically enriched substituted chiral 1-pyrroline derivatives is introduced. The strategy involves the distal functionalization of acyl heterocycles through a hydrogen-atom transfer (HAT) process and the use of tailor-made ketimines as reliable electrophilic partners. This transformation is translated into an enantiomerically controlled radical/polar cascade reaction in which water is produced as the sole by-product and stereoselectivity is dictated by coordination to a chiral-at-rhodium catalyst.

Highly Selective Hydrogenation of C═C Bonds Catalyzed by a Rhodium Hydride

Under mild conditions (room temperature, 80 psi of H2) Cp*Rh(2-(2-pyridyl)phenyl)H catalyzes the selective hydrogenation of the C═C bond in α,β-unsaturated carbonyl compounds, including natural product precursors with bulky substituents in the β position and substrates possessing an array of additional functional groups. It also catalyzes the hydrogenation of many isolated double bonds. Mechanistic studies reveal that no radical intermediates are involved, and the catalyst appears to be homogeneous, thereby affording important complementarity to existing protocols for similar hydrogenation processes.

Strategy for Catalytic Chemoselective Cross-Enolate Coupling Reaction via a Transient Homocoupling Dimer

A new strategy, a transient homocoupling dimer strategy, for direct catalytic oxidative cross-enolate coupling reactions is developed. Cross-enolate coupling products bearing a (contiguous) tetrasubstituted carbon center were obtained chemoselectively without the need for stoichiometric amounts of strong bases/metal oxidants, and thus, the present catalysis provides a general method for the synthesis of unnatural α,α-disubstituted amino acid motifs. The distinct transformation of azlactone and 2-acylimidazole units highlighted the synthetic utility of the present catalysis.

N-Heterocyclic carbene (NHC) catalyzed chemoselective acylation of alcohols in the presence of amines with various acylating reagents

This edge article reports the synthesis and full characterization including X-ray analysis of three different acylazolium ions. The reactivity of these acylazolium ions as acylating reagents of amines and alcohols is discussed. Whereas benzylamine slowly reacts with the acylazolium ions, benzyl alcohol acylation does not occur. However, upon activation of the alcohol with an N-heterocyclic carbene (NHC) as catalyst, efficient esterification is achieved. Importantly, benzylester formation is obtained in the presence of benzylamine upon selective alcohol activation by the NHC. High level DFT calculations reveal that alcohol activation occurs by strong H-bond formation between the NHC and the alcohol thereby increasing the nucleophilicity of the alcohol. For oxidatively generated acylazolium ions under NHC catalysis, the carbene has a dual role (cooperative catalysis): (a) the NHC is used for generation of the acylazolium ion and (b) the NHC is used for activation of the alcohol in the subsequent acylation step. NHC-catalyzed selective acylation of benzyl alcohol in the presence of benzylamine can also be achieved with trifluoroethyl and hexafluoroisopropylesters as acylation reagents. Moreover, an enol acetate also shows high O-selectivity as a chemoselective acetylation reagent. Kinetic and mechanistic studies are provided and some examples of the chemoselective acylation of amino alcohols are presented.

Aerobic oxidation of secondary benzylic alcohols and direct oxidative amidation of aryl aldehydes promoted by sodium hydride

We reported herein new reactivities and possible mechanistic implications of a simplest oxidant (NaH/air) uncovered on a broad range of useful transformations, including aerobic alcohol oxidations, allylic alcohol isomerizations and oxidations, cyclopropyl alcohol fragmentations, and direct aryl aldehyde oxidative amidations. These readily implementable transition-metal-free processes feature exceptional material accessibility, operational simplicity, and environmental compatibility, and add new dimensions to its synthetic utilities that are fairly robust yet had not previously been fully realized and systematically explored.