28122-82-9

Upstream product

• 104-88-1 4-chlorobenzaldehyde 
• 108-98-5 thiophenol 
• 882-33-7 diphenyldisulfane 
• 536-40-3 4-chlorobenzoic acid hydrazide 
• 591-50-4 iodobenzene 
• 7099-88-9 4-chlorophenylglyoxylic acid 
• 106-39-8 bromochlorobenzene 
• 82102-37-2 9-methyl-9H-fluorene-9-carbonyl chloride 
• 873-76-7 para-Chlorobenzyl alcohol 
• 637-87-6 1-Chloro-4-iodobenzene 
• 790-41-0 4-chlorobenzoic anhydride 
• 74-11-3 para-chlorobenzoic acid 
• 201230-82-2 carbon monoxide 
• 5285-87-0 phenyl thiocyanate 

Downstream Products

• 20849-33-6 phenyl p-chlorobenzenedithiocarboxylate 
• 98-11-3 benzenesulfonic acid 
• 74-11-3 para-chlorobenzoic acid 
• 1889-71-0 4'-chloro-2-phenylacetophenone 
• 53451-90-4 phenyl 4-trifluoromethylphenyl sulfide 
• 13343-26-5 phenyl p-chlorophenyl sulfide 
• 134-85-0 4-chlorobenzophenone 
• 62810-38-2 4-chlorophenyl 3-nitrophenyl ketone 
• 35256-82-7 (p-chlorophenyl)(m-methylphenyl)methanone 
• 882-33-7 diphenyldisulfane 
• 6833-15-4 4-chlorobenzanilide 
• 4018-82-0 4-chloro-N-(4-methoxyphenyl)benzamide 
• 39193-06-1 4,4'-dichlorobenzanilide 
• 2447-95-2 4-chloro-N-(4-tolyl)benzamide 

Relevant academic research and scientific papers

Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters

Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.

Pd-Catalyzed Double-Decarbonylative Aryl Sulfide Synthesis through Aryl Exchange between Amides and Thioesters

We report the palladium-catalyzed double-decarbonylative synthesis of aryl thioethers by an aryl exchange reaction between amides and thioesters. In this method, amides serve as aryl donors and thioesters are sulfide donors, enabling the synthesis of valuable aryl sulfides. The use of Pd/Xantphos without any additives has been identified as the catalytic system promoting the aryl exchange by C(O)-N/C(O)-S cleavages. The method is amenable to a wide variety of amides and sulfides.

Cu-Catalyzed Oxidative Thioesterification of Aroylhydrazides with Disulfides

An alternative thioesterification reaction via copper-catalyzed oxidative coupling of readily available aroylhydrazides with disulfides is developed, in which oxidative expulsion of N2 overcomes the activation barrier between the carboxylic acid derivativ

Method for preparing benzoic acid-S-phenyl ester compound through cuprous catalysis

The invention discloses a method for preparing a benzoic acid-S-phenyl ester compound shown as a formula (IV) through cuprous catalysis. The preparation method comprises the following steps of: preparing a reaction product from a benzaldehyde compound shown as a formula (I), elemental sulfur shown as a formula (II) and an iodobenzene compound shown as a formula (III) by using cuprous iodide as a catalyst, tetraethylammonium bromide as an alkali and N, N-dimethylformamide as a medium, and carrying out post-treatment on the reaction product to obtain the benzoic acid-S-phenyl ester compound, wherein the formulas are described in the specification. The method is efficient in chemical agent and low in cost; and the catalytic system has wide adaptability and is suitable for large-scale production of chemical intermediates.

Fukuyama Cross-Coupling Approach to Isoprekinamycin: Discovery of the Highly Active and Bench-Stable Palladium Precatalyst POxAP

An efficient and user-friendly palladium(II) precatalyst, POxAP (post-oxidative-addition precatalyst), was identified for use in Fukuyama cross-coupling reactions. Suitable for storage under air, the POxAP precatalyst allowed reaction between thioesters and organozinc reagents with turnover numbers of ～90000. A series of 23 ketones were obtained with yields ranging from 53 to 99%. As proof of efficacy, an alternative approach was developed for the synthesis of a key precursor of the natural product isoprekinamycin.

Decarbonylative thioetherification by nickel catalysis using air- and moisture-stable nickel precatalysts

A general, highly selective method for decarbonylative thioetherification of aryl thioesters by C-S cleavage is reported. These reactions are promoted by a commercially-available, user-friendly, inexpensive, air- and moisture-stable nickel precatalyst. The process occurs with broad functional group tolerance, including free anilines, cyanides, ketones, halides and aryl esters, to efficiently generate thioethers using ubiquitous carboxylic acids as ultimate cross-coupling precursors (cf. conventional aryl halides or pseudohalides). Selectivity studies and site-selective orthogonal cross-coupling/thioetherification are described. This thioester activation/coupling has been highlighted in the expedient synthesis of biorelevant drug analogue. In light of the synthetic utility of thioethers and Ni(ii) precatalysts, we anticipate that this user-friendly method will be of broad interest.

A synthesis of biaryl ketones via the C–S bond cleavage of thiol ester by a Cu/Ag salt

We report the synthesis of biaryl ketones via an unprecedented copper/silver catalyzed acylative cross-coupling of thiol esters with either an arylboronic acid or a potassium aryltrifluoroborate. This new method proceeds without a requisite Pd-catalyst and Cu(I)TC mediator, and is efficient, versatile, operationally simple, and accommodating functionally diverse thiol esters, arylboronic acids, and potassium aryltrifluoroborates.

Catalyst-free direct decarboxylative coupling of α-keto acids with thiols: a facile access to thioesters

A novel, efficient, and catalyst-free strategy has been initially developed for the construction of thioesters via the direct radical oxidative decarboxylation of α-keto acids with thiols, and the corresponding target products were obtained in moderate to good yields. It offers an alternative approach for the synthesis of useful diverse thioesters.

Formation of C(sp2)-S bonds through decarboxylation of α-oxocarboxylic acids with disulfides or thiophenols

Copper-catalyzed decarboxylative coupling between α-oxocarboxylic acids and diphenyl disulfides or thiophenols is presented, which provided an effective and direct approach for the preparation of useful thioesters through C(sp2)-S bond formatio

Palladium-catalyzed thiocarbonylation of aryl, vinyl, and benzyl bromides

(Chemical Equation Presented) A catalytic protocol for synthesis of thioesters from aryl, vinyl, and benzyl bromides as well as benzyl chlorides was developed using only stoichiometric amounts of carbon monoxide, produced from a solid CO precursor inside a two-chamber system. As a catalytic system, the combination of bis(benzonitrile) palladium(II) chloride and Xantphos furnished the highest yields of the desired compounds, along with the weak base, NaOAc, in anisole at 120°C. The choice of catalytic system as well as solvent turned out to be important in order to ensure a high chemoselectivity in the reaction. Both electron-rich and electron-deficient aryl bromides worked well in this reaction. Addition of 1 equiv of sodium iodide to the reaction improved the chemoselectivity with the electron-deficient aryl bromides. The thiol scope included both aryl and alkyl thiols, including 2-mercaptobenzophenones, whereby a thiocarbonylation followed by a subsequent McMurry coupling yielded differently substituted benzothiophenes. It was demonstrated that the methodology could be applied for 13C introduction into the thiophene ring.