79825-70-0

Upstream product

• 93-58-3 benzoic acid methyl ester 
• 811-98-3 d⁽⁴⁾-methanol 
• 23246-12-0 3,3,5-triphenyl-1,2,4-trioxolane 
• 93-89-0 benzoic acid ethyl ester 
• 72328-17-7 5-pentyl-3-phenyl-1,2,4-trioxolan 
• 23888-15-5 3,5-diphenyl-1,2,4-trioxacyclopentane 
• 1159923-08-6 2-(2,3-dioxo-3-phenylpropanamido)acetic acid 
• 100-51-6 benzyl alcohol 
• 100-52-7 benzaldehyde 
• 19424-29-4 4,4,5,5-tetramethyl-1,3-dioxolan-2-one 
• 98-88-4 benzoyl chloride 
• 96-49-1 [1,3]-dioxolan-2-one 
• 104-87-0 4-methyl-benzaldehyde 
• 55-21-0 benzamide 

Relevant academic research and scientific papers

Difluoroisoxazolacetophenone: A Difluoroalkylation Reagent for Organocatalytic Vinylogous Nitroaldol Reactions of 1,2-Diketones

Difluoroisoxazolacetophenone (DFIO) is developed as a new difluoroalkylation reagent that can be easily prepared from inexpensive starting materials. In situ remote C-C bond cleavage of DFIO affords γ,γ-difluoroisoxazole nitronate that undergoes base-catalyzed vinylogous nitroaldol additions to isatins, benzothiophene-2,3-dione, unsaturated-α-ketoesters, and cyclic 1,2-diketones. This organocatalytic debenzoate vinylogous nitroaldol reaction provides a new and mild approach for the preparation of various difluoroisoxazole-substituted 3-hydroxy-2-oxindoles.

Catalytic conversion of ketones to esters: Via C(O)-C bond cleavage under transition-metal free conditions

The catalytic conversion of ketones to esters via C(O)-C bond cleavage under transition-metal free conditions is reported. This catalytic process proceeds under solvent-free conditions and offers an easy operational procedure, broad substrate scope with excellent selectivity, and reaction scalability. This journal is

Dehydrogenative Coupling of Aldehydes with Alcohols Catalyzed by a Nickel Hydride Complex

A nickel hydride complex, {2,6-(iPr2PO)2C6H3}NiH, has been shown to catalyze the coupling of RCHO and R′OH to yield RCO2R′ and RCH2OH, where the aldehyde also acts as a hydrogen acceptor and the alcohol also serves as the solvent. Functional groups tolerated by this catalytic system include CF3, NO2, Cl, Br, NHCOMe, and NMe2, whereas phenol-containing compounds are not viable substrates or solvents. The dehydrogenative coupling reaction can alternatively be catalyzed by an air-stable nickel chloride complex, {2,6-(iPr2PO)2C6H3}NiCl, in conjunction with NaOMe. Acids in unpurified aldehydes react with the hydride to form nickel carboxylate complexes, which are catalytically inactive. Water, if present in a significant quantity, decreases the catalytic efficiency by forming {2,6-(iPr2PO)2C6H3}NiOH, which causes catalyst degradation. On the other hand, in the presence of a drying agent, {2,6-(iPr2PO)2C6H3}NiOH generated in situ from {2,6-(iPr2PO)2C6H3}NiCl and NaOH can be converted to an alkoxide species, becoming catalytically competent. The proposed catalytic mechanism features aldehyde insertion into the nickel hydride as well as into a nickel alkoxide intermediate, both of which have been experimentally observed. Several mechanistically relevant nickel species including {2,6-(iPr2PO)2C6H3}NiOC(O)Ph, {2,6-(iPr2PO)2C6H3}NiOPh, and {2,6-(iPr2PO)2C6H3}NiOPh·HOPh have been independently synthesized, crystallographically characterized, and tested for the catalytic reaction. While phenol-containing molecules cannot be used as substrates or solvents, both {2,6-(iPr2PO)2C6H3}NiOPh and {2,6-(iPr2PO)2C6H3}NiOPh·HOPh are efficient in catalyzing the dehydrogenative coupling of PhCHO with EtOH.

Experimental and Theoretical Studies on Gas-Phase Fragmentation Reactions of Protonated Methyl Benzoate: Concomitant Neutral Eliminations of Benzene, Carbon Dioxide, and Methanol

Protonated methyl benzoate, upon activation, fragments by three distinct pathways. The m/z 137 ion for the protonated species generated by helium-plasma ionization (HePI) was mass-selected and subjected to collisional activation. In one fragmentation path

Dichotomy of Atom-Economical Hydrogen-Free Reductive Amidation vs Exhaustive Reductive Amination

Rh-catalyzed one-step reductive amidation of aldehydes has been developed. The protocol does not require an external hydrogen source and employs carbon monoxide as a deoxygenative agent. The direction of the reaction can be altered simply by changing the solvent: reaction in THF leads to amides, whereas methanol favors formation of tertiary amines.

Highly effective C-C bond cleavage of lignin model compounds

A highly effective method is developed for the C-C bond cleavage of lignin model compounds. The inert Cα-Cβ or Cα-Cphenyl bond of oxidized lignin model compounds was successfully converted to an active ester bond through the classic organic name reaction, Baeyer-Villiger (BV) oxidation, and thus acetal esters and aryl esters were produced in high yields (up to 99%) at room temperature. Next, K2CO3 catalyzed the alcoholysis of the resulting ester products at 45 °C, affording various useful chemical platforms in excellent yields (up to 99%), such as phenols and multifunctional esters. This method uses commercially available reagents, is transition-metal free and simple, but highly effective, and involves mild reaction conditions.

Organocatalyzed Thia-Michael Addition and Sequential Inverse Electron Demanding Diels-Alder Reaction to 3-Vinyl-1,2,4- triazine Platforms

This work highlights the use of 3-vinyl-1,2,4-triazines as original thia-Michael acceptors and inverse electron demanding Diels-Alder platforms en route to new 7,8-dihydro-5H-thiopyrano[4,3-b]pyridines. The required but rather unstable propargylthiol nucleophiles were successfully generated in-situ upon an innovative DBU-catalyzed methanolysis event of the corresponding propargyl thioacetate derivatives. (Figure presented.).

Efficient and selective palladium-catalyzed direct oxidative esterification of benzylic alcohols under aerobic conditions

A highly efficient palladium-catalyzed approach for the direct oxidative esterification of benzylic alcohols with methanol and long-chain aliphatic alcohols under mild conditions has been achieved. This practical catalyst system exhibits a broad substrate scope and good functional group tolerance. Catalytic amount of Bi(OTf)3 is used as co-catalyst to improve the activity and selectivity of the reactions. A variety of esters are obtained in yields of 43–96%.

Efficient, scalable and economical preparation of tris(deuterium)- and 13C-labelled N-methyl-N-nitroso-p-toluenesulfonamide (Diazald) and their conversion to labelled diazomethane

A method for the preparation of multi-gramme quantities of N-methyl-d3-N-nitroso-p-toluenesulfonamide (Diazald-d3) and N-methyl-13C-N-nitroso-p-toluenesulfonamide (Diazald-13C) and their conversion to diazomethane-d2 and diazomethane-13C, respectively, is presented. This approach uses robust and reliable chemistry, and critically, employs readily commercially available and inexpensivemethanol as the label source. Several reactions of labelled diazomethane are also reported, including alkene cyclopropanation, phenolmethylation and α-diazoketone formation, as well as deuteriumscrambling in the preparation of diazomethane-d2 and subsequent methyl esterification of benzoic acid.

Supramolecular catalysis of esterification by hemicucurbiturils under mild conditions

Hemicucurbit[6]uril (HemiQ[6])-induced esterification of acids with CH 3OH was investigated. Esterification of the model substrate MA in the presence of different amounts of HemiQ[6] had reaction rate constants of k 0.5 = 0.18 h-1, k1.0 = 0.36 h-1 and k2.0 = 0.52 h-1. These results confirm that the reaction rate increases with the ratio of catalyst to substrate. Ineffective catalysis of MA esterification with a stoichiometric amount of MeOH suggests that the mechanism for HemiQ[6]-catalyzed esterification is solvolysis. Comparing the HemiQ[6]-catalytic kinetics of MA (4-methoxy-4-oxobut-2-enoic acid) with AA (acrylic acid) and BA (benzoic acid) shows that the catalytic activities should bear relation to the size of substrates. The different conversion of sorts of substrates in the presence of HemiQ[6] reveals that the supramolecular catalysis is favor in the conjugated structures. The inefficacy of HemiQ[12] demonstrates that the catalytic capability depends on the structure of the macrocyclic compound used.