222610-24-4

Upstream product

• 61266-36-2 methyl 4-(3-hydroxypropynyl)benzoate 
• 619-44-3 methyl 4-iodobenzoate 
• 107-19-7 propargyl alcohol 
• 619-42-1 4-methoxycarbonylphenyl bromide 

Downstream Products

• 1395896-01-1 ethyl 3-(4-(methoxycarbonyl)benzoyl)indolizine-1-carboxylate 
• 1402578-87-3 C₂₂H₂₂O₇ 
• 1402578-54-4 methyl 4-(4,4-di(ethoxycarbonyl)but-3-en-1-ynyl)benzoate 

Relevant academic research and scientific papers

Gold-Catalyzed Synthesis of 2,5-Disubstituted Oxazoles from Carboxamides and Propynals

2,5-Disubstituted oxazoles are synthesized by oxidative gold catalysis. In contrast to a reported procedure that delivers 2,4-disubstituted oxazoles starting from terminal alkynes, a switch in selectivity towards a 2,5-disubstitution is achieved by the use of propynals as starting materials. In the new reaction, the key intermediate is formed by the nucleophilic attack of the carboxamide onto a gold carbenoid, and then condensates with the more electrophilic aldehyde moiety already present in the substrate and not with the ketone that is derived from the oxygen donor. This new cyclization mode introduces a new carbonyl moiety as substituent at the 2,5-disubstituted oxazole, an attractive motive that can be found in bioactive compounds or be used for further derivatizations. (Figure presented.).

Ultrafast Electron Transfers in Organometallic Supramolecular Assemblies Built with a NIR-Fluorescent Tetrabenzoporphyrine Dye and the Unsaturated Cluster Pd3(dppm)3(CO)2+

The sodium 9,18,27,36-tetra-(4-carboxyphenylethynyl)tetrabenzoporphyrinatozinc(II) (TCPEBP) and sodium 5,10,15,20-tetra-(4-carboxyphenylethynyl)porphyrinatozinc(II) (TCPEP, for comparison purposes) salts were prepared to investigate the ionic driven host-guest assemblies made with the unsaturated redox-active cluster Pd3(dppm)3(CO)2+ ([Pd32+], dppm = Ph2PCH2PPh2 as a PF6- salt). Nonemissive dye?[Pd32+]x assemblies (x = 1-4) are formed in methanol with K1x (binding constants) values of 83 200 (TCPEBP) and 70 400 M-1 (TCPEP; average values extracted from graphical methods (Benesi-Hildebrand, Scott, and Scatchard), matching those obtained from fluorescence quenching experiments (static model)). These values are consistent with the more electron rich TCPEBP dye. This conclusion is corroborated by electrochemical data, which indicate a lower oxidation potential of the TCPEBP dye (+0.46 V) vs TCPEP (+0.70 V vs SCE) and by shorter calculated average Pd?O distances (DFT (B3LYP): 3.259 vs 3.438 ?, respectively). Using the position of the 0-0 component of the Q-bands and the electrochemical data, the excited-state driving forces for dye??[Pd32+]x → dye+??[Pd3+?][Pd32+]x-1 are estimated for TCPEBP (+1.22 V vs SCE) and TCPEP (1.08 V vs SCE). The time scale for this process occurs within the laser pulse (fwhm +??[Pd3+?][Pd32+]x-1 → dye?[Pd32+]x) occur well within 1 ps (respectively 650 and 170 fs for TCPEBP and TCPEP). Arguments are provided that the reorganization energy governs this difference.

Transition-metal-free and facile synthesis of 3-alkynylpyrrole-2,4-dicarboxylates from methylene isocyanides and propiolaldehyde

A transition-metal-free, facile and efficient method for the synthesis of 3-alkynylpyrrole-2,4-dicarboxylates from methylene isocyanides and propiolaldehyde with moderate to good yields has been developed. The direct transformation process and good tolerance of various substituents make it an alternative approach to previous protocols, and potential applications of these investigated compounds are expected with or without post-modifications.

Catalyst-Free Annulation of 2-Pyridylacetates and Ynals with Molecular Oxygen: An Access to 3-Acylated Indolizines

A catalyst and additive-free annulation of 2-pyridylacetates and ynals under molecular oxygen was the first developed, affording 3-acylated indolizines in good to excellent yields. Molecular oxygen was used as the source of the carbonyl oxygen atom in indolizines. This approach was compatible with a wide range of functional groups, and especially it has been successfully extended to unsaturated double bonds and triple bonds, which were difficult to prepare by previous methods in a single step.

Zinc-catalyzed [4+3] cycloaddition with concomitant furan annulation: Formation of cyclohepta[b]furans

A convenient zinc-promoted [4+3] cycloaddition of a carbonyl ene-yne with simple dienes was first achieved. This reaction provided an efficient strategy to prepare various cyclohepta[b]furan rings by cascade cycloadditions. Additionally, a multicomponent reaction of dione, alkynal, and diene was also reported, which exhibited a novel strategy for selective creations of C-O bonds and C-C bonds. Go tandem! A first zinc-catalyzed tandem [4+3] cycloaddition is presented herein. Various substituted cyclohepta[b]furans were synthesized from carbonyl ene-yne and diene in moderate to good yield. Furan rings and seven-membered rings were prepared in one single step (see scheme; TBS=tert-butyldimethyl).

Catalytic Asymmetric Synthesis of Alkynyl Aziridines: Both Enantiomers of cis-Aziridines from One Enantiomer of the Catalyst

Alkynyl aziridines can be obtained from the catalytic asymmetric aziridination (AZ reaction) of alkynyl imines with diazo compounds in high yields and high asymmetric inductions mediated by a chiral boroxinate or BOROX catalyst. In contrast to the AZ reaction with aryl- and alkyl-substituted imines, alkynyl imines react to give cis-substituted aziridines with both diazo esters and diazo acetamides. Remarkably, however, the two diazo compounds give different enantiomers of the cis-aziridine from the same enantiomer of the catalyst. Theoretical considerations of the possible transition states for the enantiogenic step reveal that the switch in enantiomers results from a switch from Si-face to Re-face addition to the imine, which in turn is related to a switch from reaction with an E-imine in the former and a Z-isomer of the imine in the latter. The imine did it: The aziridination of alkynyl imines with diazo esters and diazo acetamides gives cis-aziridines with very high enantioselectivities. The absolute configuration of the cis-aziridine is reversed for the two diazo compounds even though the same enantiomer of the catalyst is used. The alkynyl imines can isomerize under the reaction conditions and the enantiomeric switch is proposed to result from the preferential reaction of E-imine with diazo esters and Z-imines with diazo acetamides.

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.