Acid chlorides, coupling

Coupling of RCOCl with Buf b," In the presence of this Pd(0) complex, acid chlorides couple with Bu4Pb at 65° to form ketones, RCOBu, in high yield, with utilization of two of the four butyl groups attached to lead. 

M Beyermann, M Bienert, H Niedrich, LA Carpino, D Sadat-Aalaee. Rapid continuous peptide synthesis via FMOC amino acid chloride coupling and (4-aminome-thyl(piperidine deblocking. J Org Chem 55, 721, 1990. 

Prior to our studies trimethylsilyl (TMS) acetylene (4a) has turned out to be a notorious problem in standard acid chloride couplings and there was no report on its successful transformation. We have optimized the coupling conditions and we exemplified them for several (hetero)aroyl chlorides 7 as coupling partners (Scheme 6). It is noteworthy to mention that the yields for the corresponding Stille couplings with tributylstannyl TMS acetylene as alkyne coupling partner give with 70% (8a) [49], 51% (8b) [50], and 45% (8c) [51] substantially lower yields. 

FIGURE 8.2. Amide formation by acid chloride coupling... 

Acid chlorides couple with arylstannanes to form ketones in HMPA solution in the presence of chlo-robis(triphenylphosphinebenzyl)palladium. The same methodology has been used as part of a very efficient synthesis of manoalide and its seco derivative. The coupling of aroyl chlorides with benzylzinc bromides also produces arylbenzyl ketones under palladium catalysis.The benzylzinc bromides are formed in situ. ... 

The CuCN 2LiBr solution was cooled to -40°C and transferred into the LiNap with a cannula. The solution was stirred for 5 min. The active copper solution was warmed to -35°C and charged with ethyl 4-bromobutyrate (1.95 mmol). For aryl halides the solution was warmed to 0°C, immediately charged with the aryl halide, and allowed to mix for 1 h. The solution was stirred for 10 min and was ready to use for acid chloride couplings or conjugate additions. 

Acid chlorides Acid coupling Acid deposition... 

Pigment Red 144 [5280-784] 20735 disa2o condensation coupling of dia2oti2ed 2,5-dichloroaniline with 3-hydroxy-2-napthoic acid, foUowed by acid chloride formation and reaction with 2-chloro-/)-phen5iene- diamine... 

Claisen ester condensation, 6, 279 Thiazolecarboxylic acid chlorides reactions, 6, 279-280 Thiazolecarboxylic acid hydrazides synthesis, 6, 280 Thiazolecarboxylic acids acidity, 6, 279 decarboxylation, 6, 279 reactions, S, 92 6, 274 Thiazole-2-carboxylic acids decarboxylation, S, 92 Thiazole-4-carboxylic acids stability, S, 92 Thiazole-5-carboxylic acids decarboxylation, S, 92 Thiazole-4,5-dicarboxylic acid, 2-amino-diethyl ester reduction, 6, 279 Thiazole-4,5-dicarboxylic acids diethyl ester saponification, 6, 279 Thiazolediones diazo coupling, 5, 59 Thiazoles, 6, 235-331 ab initio calculations, 6, 236 acidity, S, 49 acylation, 6, 256 alkylation, S, 58, 73 6, 253, 256 analytical uses, 6, 328 antifogging agents... 

Piperazine, N-alkylation with benzyl chloride, 42, 19 Piperazine, 1-benzyl-, 42,19 Piperidine, addition to ethylene, 43, 45 as catalyst for Claisen-Schmidt condensation, 41, 40 Piperidine, 1-ethyl-, 43, 45 Piperidine, 1-(2-naphthyl)-, 40,74 Pivalic acid, oxidative coupling to a,a,-a, a -tetramethyladipic add, 40, 92... 

In a similar way, polyester block copolymers were obtained by reacting acid chloride-terminated polyesters with hydroxy-terminated polyethers,401 or by reacting polyester-containing polymer mixtures with coupling agents such as diisocyanates.402... 

Polylactides, 18 Poly lactones, 18, 43 Poly(L-lactic acid) (PLLA), 22, 41, 42 preparation of, 99-100 Polymer age, 1 Polymer architecture, 6-9 Polymer chains, nonmesogenic units in, 52 Polymer Chemistry (Stevens), 5 Polymeric chiral catalysts, 473-474 Polymeric materials, history of, 1-2 Polymeric MDI (PMDI), 201, 210, 238 Polymerizations. See also Copolymerization Depolymerization Polyesterification Polymers Prepolymerization Repolymerization Ring-opening polymerization Solid-state polymerization Solution polymerization Solvent-free polymerization Step-grown polymerization processes Vapor-phase deposition polymerization acid chloride, 155-157 ADMET, 4, 10, 431-461 anionic, 149, 174, 177-178 batch, 167 bulk, 166, 331 chain-growth, 4 continuous, 167, 548 coupling, 467 Friedel-Crafts, 332-334 Hoechst, 548 hydrolytic, 150-153 influence of water content on, 151-152, 154... 

Particularly, some newly developed drags, which incorporate the N-acyl sulfonamide moiety [8-10], are synthesized from the parent sulfonamides, by their coupling with acid chlorides or carboxylic anhydrides in basic conditions [11-15]. Unfortunately all these methods lead to substantial waste products. Less common reports mentioning this transformation under acidic conditions (Bronsted or Lewis acids) do not systematically examine the purpose and limitations of the reaction [16]. 

Instead of the isolated arylsulfonic acid azolides, mixtures of arylsulfonic acid chlorides and azoles have also been used for phosphorylation on a nucleoside 5 -OH or as coupling agents in the synthesis of oligodeoxyribonucleotides. 94 133 1371... 

PLLA-fr-PCL) multiblock copolymers were prepared from the coupling reaction between the bischloroformates of carboxylated PLLA with diol-terminated PCL in the presence of pyridine [140]. LLA was polymerized with SnOCt2 and 1,6-hexanediol followed by the reaction with succinic anhydride to provide the dicarboxylated PLLA. The carboxyl end groups were subsequently transformed to acid chloride groups by the reaction with thionyl chloride (Scheme 65). As expected, the molecular weight distributions were broad for all samples (1.84 < Mw/Mn < 3.17). 

Trapping experiments with electron deficient olefins such as acrylonitrile and 3-buten-2-one gave the expected 1,4-adducts from the proposed acylnickel intermediates. This provides strong support for the proposed mechanism. It was also demonstrated that allylic, vinylic and pentafluorophenyl halides could be cross-coupled with acid chlorides to give the corresponding ketones in good yields. 

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