22768-07-6

Upstream product

• 539-74-2 Ethyl 3-bromopropionate 
• 66680-87-3 (2-phenylvinyl)tributylstannane 
• 21040-45-9 Cinnamyl acetate 
• 5764-82-9 bromo(2-ethoxy-2-oxoethyl)zinc 
• 94-02-0 ethyl 3-oxo-3-phenylpropionate 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 78-39-7 Triethyl orthoacetate 
• 105-53-3 diethyl malonate 
• 588-72-7 [(E)-2-bromoethenyl]benzene 
• 140-88-5 ethyl acrylate 
• 100-42-5 styrene 
• 27374-25-0 [(1-Ethoxycyclopropyl)oxy]trimethylsilane 
• 588-73-8 (Z)-β-bromostyrene 

Downstream Products

• 109756-13-0 E-ethyl 2-methyl-5-phenylpent-4-enoate 
• 824431-51-8 5-[(E)-5-(4-Methoxy-phenyl)-pent-4-enyl]-2,2-dimethyl-5-((E)-5-phenyl-pent-4-enyl)-[1,3]dioxane-4,6-dione 
• 824431-57-4 5-[(E)-5-(4-Chloro-phenyl)-pent-4-enyl]-2,2-dimethyl-5-((E)-5-phenyl-pent-4-enyl)-[1,3]dioxane-4,6-dione 
• 824431-62-1 2,2-Dimethyl-5-[(E)-5-(4-nitro-phenyl)-pent-4-enyl]-5-((E)-5-phenyl-pent-4-enyl)-[1,3]dioxane-4,6-dione 
• 824431-60-9 2,2-Dimethyl-5-((E)-5-phenyl-pent-4-enyl)-5-[(E)-5-(4-trifluoromethyl-phenyl)-pent-4-enyl]-[1,3]dioxane-4,6-dione 
• 4266-03-9 N-Methyl-2-(phenylmethyl)pyrrolidine 
• 36939-28-3 N-methyl-2-phenylpiperidine 
• 122333-70-4 cis-N-Methyl-5-phenyl-4-penten-1-amine 
• 36884-28-3 5-phenyl-1-pentanal 
• 30154-22-4 trans-5-phenyl-4-pentenamide 
• 51498-40-9 trans-N,N-dimethyl-5-phenyl-4-penten-1-amine 
• 122333-71-5 trans-5-phenyl-4-penten-1-amine 
• 79685-62-4 5-Phenyl-4-pentenoic acid chloride 
• 131529-89-0 trans-N-Isopropyl-5-phenyl-4-penten-1-amine 

Relevant academic research and scientific papers

Diastereoselective and Stereodivergent Synthesis of 2-Cinnamylpyrrolines Enabled by Photoredox-Catalyzed Iminoalkenylation of Alkenes

A photoredox-catalyzed iminoalkenylation of γ-alkenyl O-acyl oximes has been developed. Readily available alkenylboronic acids serve as alkenylation reagents, leading to densely functionalized pyrrolines. Both (E)- and (Z)-cinnamylpyrrolines are accessible depending on the reaction solvent. In dichloromethane, (E)-cinnamylpyrrolines are produced through a photoredox-mediated single-electron-transfer process. In tetrahydrofuran, (Z)-cinnamylpyrrolines are generated by photocatalytic contra-thermodynamic E-to-Z isomerization of (E)-cinnamylpyrrolines though an energy-transfer pathway. Two stereocenters are established with complete diastereoselectivity and only one diastereomer is isolated.

Stereodivergent Nucleophilic Additions to Racemic β-Oxo Acid Derivatives: Fast Addition Outcompetes Stereoconvergence in the Archetypal Configurationally Unstable Electrophile

Additions of carbon nucleophiles to racemic α-stereogenic β-oxo acid derivatives that deliver enantiomerically enriched tertiary alcohols are valuable, but uncommon. This article describes stereodivergent Cu-catalyzed borylative cyclizations of racemic β-oxo acid derivatives bearing tethered pro-nucleophilic olefins to deliver highly functionalized cyclopentanols containing four contiguous stereogenic centers. The reported protocol is applicable to a range of β-oxo acid derivatives, and the diastereomeric products are readily isolable by typical chromatographic techniques. α-Stereogenic-β-keto esters are typically thought to have extreme or spontaneous configurational fragility, but mechanistic studies for this system reveal an unusual scenario wherein productive catalysis occurs on the same time scale as background substrate racemization and completely outcompetes on-cycle epimerization, even under the basic conditions of the reaction.

Lewis Base Catalyzed, Sulfenium Ion Initiated Enantioselective, Spiroketalization Cascade

A Lewis base catalyzed, enantioselective sulfenocyclization of alkenes to afford [6,6]spiroketals has been developed. The method uses a chiral Lewis base catalyst with an electrophilic sulfur source to generate enantioenriched thiiranium ion with alkenes. Upon formation, the thiiranium ion is subsequently captured in a cascade-type reaction, wherein a ketone oxygen serves as the nucleophile to open the thiiranium ion and an alcohol provides the secondary cyclization to form biorelevant spiroketals. A variety of electron-rich and electron-neutral E-substituted styrenes form the desired spiroketals in good yields with excellent enantio- and diastereoselectivities. Alkyl-substituted and terminal alkenes participate in the cascade reaction, but with a limited scope compared to the styrenyl substrates. This method allows for rapid formation of highly substituted spiroketals in good yield and excellent enantioselectivity.

Covalent Organic Framework as a Heterogeneous Ligand for the Regioselective Oxidative Heck Reaction

A simple imine-based covalent organic framework (COF) as heterogeneous ligand for PdII-promoted Heck reaction is reported. Good regioselectivity for a wide range of electronically unbiased olefins is obtained (linear/branched >100:1 in most cases). Related tests and density functional theory calculations are used to explore the reason underlying the high selectivity. This research opens a route for COF as an intriguing platform to control regioselectivity catalysis.

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

A weakly coordinating monodentate heteroaryl thioether directing group has been developed for use in Pd(II) catalysis to orchestrate key elementary steps in the catalytic cycle that require conformational flexibility in a manner that is difficult to accom

Catalytic hydrogenation of α,β-unsaturated carboxylic acid derivatives using copper(i)/N-heterocyclic carbene complexes

A simple and air-stable copper(i)/N-heterocyclic carbene complex enables the catalytic hydrogenation of enoates and enamides, hitherto unreactive substrates employing homogeneous copper catalysis and H2 as a terminal reducing agent. This atom economic transformation replaces commonly employed hydrosilanes and can also be carried out in an asymmetric fashion.

Dehydrative Synthesis of Functionalized Skipped Dienes from Stabilized Phosphonium Ylides and Allylic Alcohols in Water

A mild and extra activator-free dehydrative alkylation of stabilized phosphonium ylides with allylic alcohols in water is developed in the presence of [Pd(allyl)Cl]2/dppf catalyst. A wide range of aryl, heteroaryl, alkyl and even allylic tertiary alcohols can readily react with stabilized phosphonium ylides with high regioselectivity for the efficient synthesis of functionalized skipped dienes in moderate to high yields. The role of water was investigated by means of a high-resolution mass spectrum and diffusion-ordered spectroscopy nuclear magnetic resonance, and the results revealed that water might play a crucial role in the formation of the π-allylpalladium complex via hydrogen bond. However, the present method is not suitable for water-sensitive phosphonium ylides. (Figure presented.).

Arene Trifunctionalization with Highly Fused Ring Systems through a Domino Aryne Nucleophilic and Diels–Alder Cascade

A convenient and efficient domino aryne process was developed under transition-metal-free conditions to generate a range of tetra- and pentacyclic ring systems. This transformation was realized via a 1,2-benzdiyne through a nucleophilic and Diels–Alder reaction cascade using styrene as the diene moiety. Three new chemical bonds, namely one C?N and two C?C bonds, and two benzofused rings could be constructed concomitantly, which was made possible by distinct chemoselective control at both the 1,2-aryne and 2,3-aryne stages. Moreover, in-depth studies were carried out on the domino aryne precursors and controlling the diastereoselectivity.

Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

Rapid Access to Thiolactone Derivatives through Radical-Mediated Acyl Thiol-Ene and Acyl Thiol-Yne Cyclization

A new synthetic approach to thiolactones that employs an efficient acyl thiol-ene (ATE) or acyl thiol-yne (ATY) cyclization to convert unsaturated thiocarboxylic acid derivatives into thiolactones under very mild conditions is described. The high overall yields, fast kinetics, high diastereoselectivity, excellent regiocontrol, and broad substrate scope of these reaction processes render this a very useful approach for diversity-oriented synthesis and drug discovery efforts. A detailed computational rationale is provided for the observed regiocontrol.