Carboxylic acid chlorides arylation

In analogy to the active esters, thioesters are prepared by condensation of thiols with carboxylic acids/DC(3 or carboxylic acid chlorides. " Aryl thioesters react readily with nucleophiles like amines to give amides. Peptides are prepared without racemization. In the case of r-butyl thioesters activation is accomplished by treatment with Ag02CCp3. 

The course of the reaction of phosphinous amides with carboxylic acid chlorides is dependent on the characteristics of the iV-residue. Thus with N-aryl compounds this reaction gives chlorophosphanes and carboxamides. With AT-alkyl analogs the primary reaction products have not been identified but they hydrolyzed to carboxaldehydes [120]. 

Monosubstituted and 4,5-disubstituted oxazoles were easily obtained from aryl-substituted tosylmethyl isocyanides and aldehydes . Tosyloxazoles 107, prepared from TosMIC 106 and carboxylic acid chlorides, led to 5-substituted derivatives 108 through ultrasound-promoted desulfonylation <00JCS(P1)527>. 

Vinyl Substitutions with Carboxylic Acid Halides, Aryl Sulflnates and Arylsulfonyl Chlorides 856... 

Grignard reagents derived from aryl bromides are readily prepared and may be converted into organocadmium compounds by treatment with cadmium chloride (cf. Section 5.8.4, p. 616). Reaction of an organocadmium with a carboxylic acid chloride constitutes a convenient synthesis of aryl alkyl ketones. 

Arenetellurinic chlorides and carboxylic acid chlorides in refluxing carbon tetrachloride produced aryl tellurium trichlorides and carboxylic acid anhydrides3. 

A promising method for the synthesis of unsymmctrical diorgano tellurium compounds uses carboxylic acid derivatives and diaryl ditellurium as starting materials. The carboxylic acid chloride, prepared in quantitative yield from the acid and oxalyl chloride is added slowly to a mixture of a diary] ditellurium and the sodium salt of 2-mercaptopyridine N-oxide in toluene at 35°. Under normal laboratory light the aryl tellurium radicals... 

Preparation of phosphorus ylides Elimination of nitrous acid Steric control of elimination reactions. Mdol condensation Rearrangements Reactions with aryl isocyanates Preparation of carboxylic acid chlorides Synthesis of macromolecules... 

Methylisoxazole-5-carboxylic acid was converted into the corresponding 5-carboxamides and 5-(l/7-pyrazol-l-ylcarbonyl) derivatives in satisfactory yields by treatment with thionyl chloride and amines or pyrazoles <2002SC425>. A three-component assembly of isoxazole-5-carboxylic acid chloride, 1,1-dimethylallene, and bis-pinacolatodiboron, catalyzed by a phosphine-free palladium complex, gave 2-acylallylboronate derivatives regiose-lectively (Equation 47) <2003JA12576>. On the other hand, a mild procedure allowed the preparation of /3,7-unsaturated ketones by simple reaction of 3-aryl-5-methylisoxazole-4-carboxylic acid chlorides with allyl bromide and indium in DMF (Equation 48) <1997TL8745>. 

Pyrazolo[3,4-Z)]pyridines, the 7-chloro-6-fluoro-2,4-dimethylquinoline and its mercapto-thiadiazolyl or oxadiazolyl quinolines 21 were prepared via Diels-Alder reaction conversion of methyl 2-(3-oxo-3-phenylpropenylamino)benzoate into 3-benzoyl-l.S -quinolin-4-one 22 . A mixture of aniline derivatives and malonic ester gave a variety of 3-aryl-4-hydroxyquinolin-2(l//)-ones 23. Condensation of isatins with ketones afforded quinoline-4-carboxylic acids. 2-Aryl-l,2,3,4-tetrahydro-4-quinolinones 22 and carbazolylquinolone were also prepared. The substitution of 2-chloroquinoline gave the 2-substituted quinolines. Basic alumina has catalyzed the C-C bond formation between 2-hydroxy-1,4-naphthoquinone and 2-chloroquinoline derivative to give 21. Reaction of organic halides with 8-hydroxyquinolines gave the respective ethers. The azodye derivatives of 21 were prepared in the absence of solvent. Silica gel catalyzed the formation of 2-ketomethylquinolines from reaction of 2-methylquinolines with acyl chlorides. 

A clear illustration of the advantages of this synthetic procedure is provided by the conversion of diethyl 1-fluoro-l-(ethoxycarbonyl)-2-aryl-2-oxoethylphosphonates into the corresponding a-fluoro-p-keto esters. Because of the sensitive nature of the P-C bond, the reaction proceeds smoothly at room temperature by the MgCl2-induced P-C bond cleavage in diethyl 1-fluoro-1-(ethoxycar-bonyl)-2-aryl-2-oxoethylphosphonates, readily obtained by the reaction of diethyl 1-fluoro-l-(ethoxycarbonyl)methyIphosphonate with aromatic carboxylic acid chlorides (Scheme 7.28). ... 

In the presence of a base, the difunctional 4-chloropyrimidine-5-carboxylic acid chloride reacts in an acylation-arylation sequence with Ar-monosubstituted enamines to give 6,7,8-trisubstituted pyrido[2,3-oT pyrimidin-5(8//)-ones 19.162... 

A complex consisting of Cu 1.10-phenanthroline [which mediates decarboxylation of arylcarboxylic acids with formation of aryl Cu species] and Pd(acac)2 [for coupling] was made and used to catalyse the decarboxylative cross-coupling of the Cu species with aryl halides. This bimetallic system allows direct coupling of a variety of aryl, heteroaryl or vinyl carboxylic acids with aryl or heteroaryl bromides, chlorides or iodides at 160° in N methylpyrrolidine in the presence of K2CO3. [Goossen et al. JAm Chem Soc 129 4824 2007]. 

Ghlorotris(triphenylphosphine) rhodium causes the decarbonylation of aroyl to aryl chlorides in excellent yields at relatively low temp. At higher temp., only catalytic amounts of the reagent are required. — E A mixture of henzoyl chloride, the above Rh-compound, and benzene heated 15 min. at 80° chlorobenzene. Y almost 100%. F. e. s. J. Blum, Tetrah. Let. 1966, 1605 chlorides from sulfonic acid chlorides s. Tetrah. Let. 1966, 3041 also ethylene derivatives from carboxylic acid chlorides s. J. Tsuji and K. Ohno, Am. Soc. 88, 3452 (1966) Tetrah. Let. 1966, 4713. 

The reaction of carboxylic acid chlorides with low-valent metal complexes leads to the formation of acyl complexes, which can undergo decarbonylation to give a-bonded metal alkyls, alkenyls, or aryl complexes. This decarbonylation has been used to synthesize aiylsilanes from aryl acid chlorides in the presence of nickel(0) or palladium(0) complexes as catalysts. Similarly, acyl cyanides undergo decarbonylation with palladium(O) complexes to afford nitriles or alkenes, depending on the substrate. ... 

The chelate-stabilized, electron-rich Pd(0) complex, (dippp)2Pd(0) 6 (Scheme 8) was an efficient catalyst for carbonylation of aryl chlorides. Alper reported that bis(tricyclo-hexylphosphine)paUadium dichloride is an active catalyst for the carbonylation of aryl chlorides to carboxylic acid. Neat aryl chlorides reacted with carbon monoxide and aqueous KOH in the presence of catalytic amounts of this catalyst to give the corresponding carboxylic acids upon subsequent acidification. The Pd-catalyzed amidalion of electron-deficient aryl chloride readily afforded a carbonylation prodnct in the presence of low CO pressure and a slight excess of an iodide salt. Alkoxycarbonylation of aryl chlorides using palladium catalyst Pd(PCy3)2(dba) has been reported. ... 

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