937-53-1

Upstream product

• 1817-57-8 4-phenyl-3-butyne-2-one 
• 100-52-7 benzaldehyde 
• 32398-66-6 1-phenylbut-2-yn-1-ol 
• 1896-62-4 (E)-benzalacetone 
• 142-82-5 n-heptane 
• 60-29-7 diethyl ether 
• 540-84-1 2,2,4-trimethylpentane 
• 917-54-4 methyllithium 
• 80783-99-9 3-phenyl-N-methoxy-N-methylacrylamide 
• 536-74-3 phenylacetylene 
• 1486-28-8 diphenyl(methyl)phosphine 
• 78-95-5 chloroacetone 
• 67-64-1 acetone 
• 6738-06-3 phenylethynylmagnesium bromide 

Downstream Products

• 16301-92-1 (3-oxo-1-phenylbutyl)diphenylphosphine sulfide 
• 116145-00-7 C₁₀H₉⁽²⁾HO 
• 30262-96-5 4-phenyl-4-trimethylsilylbutan-2-one 
• 1896-62-4 (E)-benzalacetone 
• 32147-21-0 (3E)-3-bromo-4-phenyl-3-buten-2-one 
• 139527-09-6 9-Oxo-7-phenyl-decanenitrile 
• 108070-92-4 (Z)-<(Z)-benzylideneacetone> oxime O-methyl ether 
• 108054-91-7 (E)-<(Z)-benzylideneacetone> oxime O-methyl ether 
• 54157-33-4 (Z)-pent-1-en-3-ynyl-benzene 
• 26175-42-8 (4-phenethyl-thiazol-2-yl)-phenyl-amine 
• 26175-40-6 4-phenethyl-thiazol-2-ylamine 
• 57539-17-0 1-benzyl-4-methyl-2r,5-diphenyl-2,3-dihydro-1H-phosphole 1c-oxide 
• 30204-45-6 7-hydroxy-7-methyl-5-phenyl-5H-2,3,6,7-tetrahydrothiazolo[2,3-a]pyrimidine 

Relevant academic research and scientific papers

Enantioselective Michael Addition of Photogenerated o-Quinodimethanes to Enones Catalyzed by Chiral Amino Acid Esters

The first example of a photoexcitated amine-catalyzed process for asymmetric Michael addition of o-quinodimethanes to enones is described. In the presence of simple chiral amino acid esters, a variety of Michael adducts were generally obtained in good yie

Introducing the Dihydro-1,3-azaboroles: Convenient Entry by a Three-Component Reaction, Synthetic and Photophysical Application

The (Fmes)BH2·SMe2 reagent (7) reacts sequentially with an acetylene and, e.g., xylylisonitrile in a convenient three-component reaction to give a series of unprecedented dihydro-1,3-azaborole derivatives 16. The tolane-derived example 16a was deprotonated and used as a ligand in organometallic chemistry. Compounds 16 served as the starting materials for the straightforward synthesis of various dihydro-1,3-azaborinine derivatives by treatment with an isonitrile. Several diaryldihydro-1,3-azaboroles showed interesting photophysical properties such as aggregation-induced emission and high fluorescence quantum yields.

Heterogeneous Isomerization for Stereoselective Alkyne Hydrogenation to trans-Alkene Mediated by Frustrated Hydrogen Atoms

Stereoselective production of alkenes from the alkyne hydrogenation plays a crucial role in the chemical industry. However, for heterogeneous metal catalysts, the olefins in cis-configuration are usually dominant in the products due to the most important and common Horiuti-Polanyi mechanism involved over the metal surface. In this work, through combined theoretical and experimental investigations, we demonstrate a novel isomerization mechanism mediated by the frustrated hydrogen atoms via the H2 dissociation at the defect on solid surface, which can lead to the switch in selectivity from the cis-configuration to trans-configuration without overhydrogenation. The defective Rh2S3 with exposing facet of (110) exhibits outstanding performance as a heterogeneous metal catalyst for stereoselective production of trans-olefins. With the frustrated hydrogen atoms at spatially separated high-valence Rh sites, the isolated hydrogen mediated cis-to-trans isomerization of olefins can be effectively conducted and the overhydrogenation can be completely inhibited. Furthermore, the bifunctional Rh-S/Pd nanosheets have been synthesized through the surface modification of Pd nanosheets with rhodium and sulfide. With the selective semihydrogenation of alkynes into cis-olefins catalyzed by the small surface PdSx ensembles, the bifunctional Rh-S/Pd nanosheets exhibit excellent activity and stereoselectivity in the one-pot alkyne hydrogenation into trans-olefin, which surpasses the most reported homogeneous and heterogeneous catalysts.

Z-Selective phosphine promoted 1,4-reduction of ynoates and propynoic amides in the presence of water

Phosphine-mediated reductions of substituted propynoic esters and amides in the presence of water yield the partially reduced α,β-unsaturated esters and amides with highZ-selectivity. The competitivein situ ZtoE-isomerization of the product in some cases lowers theZtoEratios of the isolated α,β-unsaturated carbonyl products. Reaction time and the amounts of phosphine and water in the reaction mixture are the key experimental factors which control the selectivity by preventing or reducing the rates ofZ- toE-product isomerization. Close reaction monitoring enables isolation of theZ-alkenes with high selectivities. The computational results suggest that the reactions could be highlyZ-selective owing to the stereoselective formation of theE-P-hydroxyphosphorane intermediate.

Synthetic Entry to Polyfunctionalized Molecules through the [3+2]-Cycloaddition of Thiocarbonyl Ylides

Here we present a comprehensive study on the [3+2]-cycloaddition of thiocarbonyl ylides with a wide variety of alkenes and alkynes. The obtained dihydro- and tetrahydrothiophene products serve as exceptionally versatile intermediates providing access to thiophenes, dienes, dendralenes, and vic-quarternary carbon centers. The use of high-pressure conditions enables thermally unstable, sterically encumbered or moderately reactive substrates to undergo the cycloaddition under mild conditions, thereby increasing the yield by up to 58percent. In addition, we showcase its utility by the formal syntheses of the pharmaceuticals NGB 4420 and tenilapine.

Stereospecific Decarboxylative Nazarov Cyclization Mediated by Carbon Dioxide for the Preparation of Highly Substituted 2-Cyclopentenones

Highly substituted 2-cyclopentenones were stereospecifically and regioselectively constructed with high catalytic efficiency through Lewis-acid catalyzed decarboxylative Nazarov cyclization of the cyclic carbonate derivative, which is prepared by reacting the propargyl alcohol with carbon dioxide in the presence of a silver catalyst. The stereochemistry of the 2-cyclopentenone is strictly controlled by the geometry of the alkene in the starting material. This method is applicable for various substrates.

Z- and E-selective Horner–Wadsworth–Emmons reactions

In the present work, we determined and evaluated the stereochemical outcome of the Horner–Wadsworth–Emmons (HWE) reaction of 2-oxoalkylphosphonates with different ester functions (bis(2,2,2-trifluoroethyl), 2,2,2-trifluoroethyl methyl, dimethyl) and side chains (aliphatic, aromatic) with three different aldehydes (benzaldehyde, THP- and PPB-protected Corey aldehydes) under two reaction conditions. The “trans” protocol is generally used in the E-selective HWE reactions, while “cis” protocol promotes the Z-selectivity.

Application of Pd Nanoparticles Supported on Mesoporous Hollow Silica Nanospheres for the Efficient and Selective Semihydrogenation of Alkynes

Herein, the preparation of a heterogeneous catalyst consisting of 1-2 nm sized Pd nanoparticles supported on amino-functionalized mesoporous hollow silica nanospheres and its use for the semihydrogenation of mono- And disubstituted alkynes is reported. By utilizing this Pd nanocatalyst together with the green poisoning agent DMSO, high yields of the desired alkenes could be achieved, while suppressing the degree of over-reduction to alkanes. To our delight, the Pd nanocatalyst displayed remarkable chemoselectivity towards the alkyne moiety, allowing the transformation to be carried out in the presence of other reducible functionalities, such as halogens, carbonyl, and nitro groups.

Selective Hydrogenation of Functionalized Alkynes to (E)-Alkenes, Using Ordered Alloys as Catalysts

Intermetallic Pd3Pb acts as a highly selective alkyne semihydrogenation catalyst that is greatly superior to the conventional Lindlar catalyst. Density functional theory (DFT) calculations demonstrate an ideal adsorption property of Pd3Pb, where the surface holds alkynes while releasing alkenes. A tandem catalytic system that is comprised of Pd3Pb/SiO2 for alkyne semihydrogenation and RhSb/SiO2 for alkene isomerization allows one-pot (E)-alkene synthesis from a functionalized alkyne, which is the first success using heterogeneous catalysts. A variety of functionalized alkynes with aldehyde, ketone, carboxylic acid, and ester moieties are hydrogenated into the corresponding (E)-alkene in good to excellent yields under 1 atm H2 at room temperature.

Green semi-hydrogenation of alkynes by Pd@borate monolith catalysts under continuous flow

Palladium nanoparticles were immobilized onto an unconventional polymeric borate macroporous monolith and the resulting mesoreactor (i.d. 3 mm, length 25 mm) used in liquid-phase catalytic semi-hydrogenation reaction of substituted alkynes under continuous flow. The catalytic system showed excellent efficiency, both in terms of activity and selectivity, and long-term stability under mild reaction conditions (methanol, room temperature, 1.5 bar H2 max), with no need of additives. Particularly, the leaf alcohol cis-3-hexen-1-ol was for the first time obtained with selectivity comparable to that of the industrial batch process. The performance of the catalyst is discussed and compared with those of the analogous batch and industrial processes.