74714-06-0

Upstream product

• 67-63-0 isopropyl alcohol 
• 2216-94-6 phenylpropynoic acid ethyl ester 
• 591-50-4 iodobenzene 
• 96088-62-9 isopropyl propiolate 
• 108-23-6 isopropyl chloroformate 
• 536-74-3 phenylacetylene 
• 71-43-2 benzene 
• 637-44-5 phenylpropyolic acid 
• 201230-82-2 carbon monoxide 

Downstream Products

• 904893-06-7 Ni₂(C₅H₅)2(CO)2 
• 81141-83-5 C₅H₅Ni(C₆H₅C₂CO₂CH(CH₃)2)NiC₅H₅ 
• 79839-04-6 C₅H₅Ni(C₆H₅C₂CO₂CH(CH₃)2)Mo(CO)2C₅H₅ 
• 79816-41-4 C₅H₅Ni(C₆H₅C₂CO₂CH(CH₃)2)Co(CO)3 
• 96095-83-9 Co₂(CO)6(PhC₂CO₂-i-Pr) 
• 1393658-26-8 propan-2-yl 3-phenylimidazo[1,2-a]pyridine-2-carboxylate 
• 60512-85-8 (E)-isopropyl cinnamate 
• 22767-95-9 1-methylethyl 3-phenylpropionoate 
• 28541-01-7 (Z)-isopropyl 3-phenylacrylate 
• 217473-61-5 (Z)-3-Phenyl-3-phenylamino-acrylic acid isopropyl ester 

Relevant academic research and scientific papers

Rhodium-catalyzed C(sp2)-H addition of arylboronic acids to alkynes using a boron-based, convertible ortho-directing group

Temporary modification of a boronyl group with pyrazoryl-aniline allowed insertion of arylpropiolates and diphenylacet-ylenes into the o-C-H bond of arylboronic acids in the presence of rhodium catalysts, giving 3,3-diarylacrylates and triarylethene conta

trans-Selective hydrocyanation of ynoates, ynones and ynoic acids catalyzed by nucleophilic phosphines

trans-Selective hydrocyanation of ynoates and ynones in the presence of TMSCN and an alcohol additive are catalyzed by nucleophilic phosphines. The trisubstituted E-olefin products of anti-addition of hydrogen cyanide to the alkyne are produced with high regio- and stereoselectivity. The alcohol additive reacts with TMSCN to produce hydrogen cyanide in situ. Ynoic acids undergo the phosphine catalyzed hydrocyanation in the presence of TMSCN under aprotic conditions only. In these reactions, TMSCN reacts with the acid to generate hydrogen cyanide and the silyl ester which, unlike the acid, undergoes phosphine catalyzed hydrocyanation and gives the stereo-defined E-2-cyano-acrylic acids after work up.

Organocatalytic trans Phosphinoboration of Internal Alkynes

We report the first trans phosphinoboration of internal alkynes. With an organophosphine catalyst, alkynoate esters and the phosphinoboronate Ph2P-Bpin are efficiently converted into the corresponding trans-α-phosphino-β-boryl acrylate products in moderate to good yield with high regio- and Z-selectivity. This reaction operates under mild conditions and demonstrates good atom economy, requiring only a modest excess of the phosphinoboronate. X-ray crystallography experiments allowed structural assignment of the unprecedented and densely functionalized (Z)-α-phosphino-β-boryl acrylate products.

Copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters with chiral phenol–carbene ligands

A chiral phenol–NHC ligand enabled the copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters. The phenol moiety of the chiral NHC ligand played a critical role in producing the enantiomerically enriched products. The catalyst worked well for various (Z)-isomer substrates. Opposite enantiomers were obtained from (Z)- and (E)-isomers, with a higher enantiomeric excess from the (Z)-isomer.

Efficient Access to Chiral β-Borylated Carboxylic Esters via Rh-Catalyzed Hydrogenation

Rh/bisphosphine?thiourea ligand (ZhaoPhos)-catalyzed asymmetric hydrogenation of (Z)-β-substituted-β-boryl-α,β-unsaturated esters was successfully developed, furnishing a variety of chiral β-borylated carboxylic esters with high yields and excellent enantioselectivities (up to 99% yield and >99% ee). The gram-scale asymmetric hydrogenation was performed efficiently in the presence of only 0.05 mol% (S/C=2 000) catalyst loading with full conversion, 99% yield and 99% ee. Moreover, the hydrogenation product was easily converted to other versatile synthetic intermediates, such as methyl (S)-3-hydroxy-3-phenylpropanoate and methyl (S)-3-(furan-2-yl)-3-phenylpropanoate. (Figure presented.).

Synthesis of Chiral β-Borylated Carboxylic Esters via Nickel-Catalyzed Asymmetric Hydrogenation

The highly efficient Ni-catalyzed asymmetric hydrogenation of β-boronic ester substituted-α,β-unsaturated carboxylic esters was successfully developed using (S,S)-Ph-BPE as the ligand. A series of chiral β-borylated carboxylic esters were obtained with high yields (94%-99% yields) and excellent enantioselectivities (89%-99% ee). The gram-scale asymmetric hydrogenation with a low catalyst loading (0.25 mol %) and synthetic transformation of hydrogenation product demonstrated the great synthetic utility of this methodology.

Oxidative Alkoxycarbonylation of Alkynes by Means of Aryl α-Diimine Palladium(II) Complexes as Catalysts

The straightforward in situ synthesized bis(2,6-diisopropyl)acenaphthenequinonediimine palladium triflate catalyst was generally employed for both the mono-alkoxycarbonylation of terminal alkynes, and the bis-alkoxycarbonylation of 1,2-disubstituted alkynes by using mild reaction conditions [carbon monoxide pressure (PCO)=4 bar, temperature=20 °C]. Utilizing low catalyst loading (down to 0.5 mol%), a variety of propiolic esters were synthesized with good to excellent isolated yields. Most importantly the system was very efficient not only with methanol but also with a range of different alcohols, starting from the less hindered benzyl alcohol to the most hindered ones, such as isopropyl alcohol and tert-butyl alcohol. In addition, aromatic and aliphatic 1,2-disubstituted alkynes were converted into maleic acid derivatives, together with an acid-catalyzed isomerization reaction, showing modest to good selectivity and excellent combined yields. In particular 3-hexyne showed a satisfactory degree of selectivity for the maleic diesters of methanol and benzyl alcohol, obtaining the corresponding products with good isolated yields. (Figure presented.).

A Simple and Efficient Esterification Method

A convenient and practical esterification was realized and this reaction proceeded without a dehydrating reagent or water removal equipment. The synthesis of esters by reaction of carboxylic acids with various alcohols such as methyl, ethyl, isopropyl, isobutyl, allyl, benzyl, propargyl and decanyl alcohols were achieved with a catalytic amount of CBr4 under refluxing reaction condition.

Palladium-catalyzed carbonylation of terminal acetylenes: A new method for synthesis of acetylenecarboxylates

Acetylenecarboxylates were easily prepared via palladium bromide-catalyzed carbonylation of terminal acetylenes in fair to good yields.

Enantioselective Catalytic Epoxidation of Cinnamate Esters

A broad study of the (salen)Mn(III)-catalyzed asymmetric epoxidation of cis-cinnamate esters reveals that the steric properties of the ester group have a profound influence on enantioselectivity in the epoxidation reaction, with bulkier esters affording highest ee's.The sensitivity of the reaction selectivity to the steric properties of the cis-alkene are consistent with a "skewed" side-on approach of olefin to the metal -oxo.The electronic properties of the substrate arene ring substituents do not correlate with epoxidation ee, but instead with the cis/trans partitioning of product formation.Evidence is provided for a non-polar inter mediate in a stepwise oxygen-atom-transfer mechanism.The presence of pyridine N-oxide derivatives has a significant effect on catalysts rates and total turnovers, but negligible influence on the stereoselectivity of epoxidation.A mechanistic basis for the role of these additives is proposed.The synthetic applicability of the cinnamate epoxidation methodology is illustrated in the highly enantioslective synthesis of diltiazem.