154884-62-5

Upstream product

• 50-00-0 formaldehyd 
• 90585-32-3 1,1-dibromo-2-(2-methoxyphenyl)ethene 
• 107-19-7 propargyl alcohol 
• 578-57-4 2-bromoanisole 
• 529-28-2 4-iodoanisol 
• 850079-46-8 [3-(2-methoxy-phenyl)-prop-2-ynyloxy]-trimethyl-silane 

Downstream Products

• 154884-63-6 3-(2-methoxyphenyl)propiolaldehyde 
• 1235983-68-2 diisopropyl 1-(3-(2-methoxyphenyl)-2-propyn-1-yl)hydrazine-1,2-dicarboxylate 
• 1367053-90-4 (R)-2-(2-methoxyphenyl)-4-(nitromethyl)-4H-chromene-3-carbaldehyde 
• 1504-61-6 (E)-3-(2-methoxyphenyl)prop-2-en-1-ol 
• 163267-95-6 (E)-1-(3-chloroprop-1-en-1-yl)-2-methoxybenzene 
• 1067906-24-4 3-(allyloxy)-1-(2-methoxyphenyl)-1-propyne 

Relevant academic research and scientific papers

Unexpected Course of the Reaction of 1,3-Bis(dimethylamino)trimethinium Perchlorate with 3-Substituted Prop-2-ynals Leading to 1-Aryl-2,4,6-triformylbenzenes

Reaction of 1,3-bis(dimethylamino)trimethinium perchlorate (1) with 3-substituted prop-2-ynals (4) in acetic anhydride at the presence of ZnBr2 gives upon hydrolysis 1-substituted 2,4,6-triformylbenzenes (6) in low to moderate yield. This reaction is restricted to prop-2-ynals bearing electron rich aromatic substituents at the 3-position.

Enantioselective Nickel-Catalyzed Alkyne-Azide Cycloaddition by Dynamic Kinetic Resolution

The triazole heterocycle has been widely adopted as an isostere for the amide bond. Many native amides are α-chiral, being derived from amino acids. This makes α-N-chiral triazoles attractive building blocks. This report describes the first enantioselective triazole synthesis that proceeds via nickel-catalyzed alkyne-azide cycloaddition (NiAAC). This dynamic kinetic resolution is enabled by a spontaneous [3,3]-sigmatropic rearrangement of the allylic azide. The 1,4,5-trisubstituted triazole products, derived from internal alkynes, are complementary to those commonly obtained by the related CuAAC reaction. Initial mechanistic experiments indicate that the NiAAC reaction proceeds through a monometallic Ni complex, which is distinct from the CuAAC manifold.

One-pot synthesis of 3-substituted-4H-[1,2,3] triazolo[5,1-c][1,4]oxazin-6(7H)-ones from propargyl alcohols, chloroacetyl chloride, and sodium azide

An efficient, one-pot synthesis of 3-substituted-4H-[1,2,3]triazolo[5,1-c][1,4]oxazin-6(7H)-ones is developed via sequential esterification, substitution, and 1,3-dipolar cycloaddition processes of various propargyl alcohols, chloroacetyl chloride, and so

Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes

Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cla￠ radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.

Rhodium(i)-catalyzed Pauson-Khand-type reaction using formic acid as a CO surrogate: An alternative approach for indirect CO2 utilization

Formic acid is found to be an ideal CO surrogate for the rhodium(i)-catalyzed Pauson-Khand-type (PK-type) reaction of various substituted 1,6-enynes to afford bicyclic cyclopentenones in moderate to good yields. High TON value of up to 263 and good results in the gram-scale experiment were also obtained, demonstrating the efficacy of this methodology. In addition, heterocyclic molecules of pharmaceutical importance were also furnished via inter- or intra-molecular hetero-PK-type reactions, further broadening the application of current strategy. In this protocol, formic acid was utilized as a bridging molecule for the conversion of CO2 to CO, since formic acid is manufactured via catalytic hydrogenation of CO2 and releases CO in the presence of acetic anhydride readily. Therefore, this methodology represents a green and indirect approach for chemical valorization of CO2 in the preparation of value-added compounds.

Metal-free aminothiation of alkynes: Three-component tandem annulation toward indolizine thiones from 2-alkylpyridines, ynals, and elemental sulfur

A metal-free three-component annulation reaction for the synthesis of indolizine thiones via tandem C-C/C-N/C-S bond formation was developed. Various 2-alkylpyridines with aromatic ynals and elemental sulfur proceeded smoothly under catalyst-free conditions, and the desired products were obtained in moderate to excellent yields.

Bi(OTf)3 catalyzed synthesis of acyclic β-sulfanyl ketones via a tandem Meyer-Schuster rearrangement/conjugate addition reaction

A new strategy to prepare acyclic β-carbonyl thioethers from propargyl alcohols and sulfur nucleophiles is reported. The investigation of the reaction substrates scope indicated that primary 3-aryl propargyl alcohols and thiols underwent the transformation smoothly. The reaction probably proceeded a Bi(OTf)3-catalyzed tandem Meyer-Schuster rearrangement of 3-aryl propargyl alcohol, followed by a thiol Michael conjugate addition of thiols to in situ generated α, β-unsaturated ketones. The method was 100% atom economic, high-yielding, and easy to handle, making it a valuable method for the construction of β-carbonyl sulfides.

Cobalt-catalyzed (Z)-selective semihydrogenation of alkynes with molecular hydrogen

Cobalt-catalyzed highly (Z)-selective semihydrogenation of alkynes using molecular H2 was developed using commercially available and cheap cobalt precursors. A variety of (Z)-alkenes were obtained in moderate to excellent selectivities [(Z)-alkene/(E)-alkene/alkane ratio up to >99 : 1 : 1] and it was found that the readily available ethylenediamine ligand is crucial in determining the selectivity.

Fe(OTf)3-catalyzed tandem Meyer-Schuster rearrangement/intermolecular hydroamination of 3-aryl propargyl alcohols for the synthesis of acyclic β-Aminoketones

Fe(OTf)3-catalyzed synthesis of acyclic β-aminoketones from 3-aryl propargyl alcohols and nitrogen nucleophiles were investigated. Results showed that propargyl alcohols without bulky groups α to the hydroxyl group underwent the transformation smoothly. Sulphonamides exhibited the higher reactivity than amides as the nitrogen nucleophiles and the transformation of acyclic β-aminoketones were finished in shorter reaction time and higher yields. Finally, racemic fluoxetine was efficiently accessed with the present reaction as the first step. This novel synthesis of acyclic β-aminoketones probable proceeded a Fe(OTf)3-catalyzed Meyer-Schuster rearrangement of 3-aryl propargyl alcohols, followed by a intermolecular hydroamination between nitrogen nucleophiles and α, β-unsaturated ketones.

3-ARYL PROPIOLONITRILE COMPOUNDS FOR THIOL LABELING

The present invention relates to a process for labeling compounds comprising thiol moieties with 3-arylpropiolonitrile compounds, to 3-arylpropiolonitrile compounds substituted with tag moieties and to specific 3-arylpropiolonitrile linkers.