Acyl chlorides coupling reactions

Acylation and Coupling Reactions. Reagents used for the preparation of unsymmetrical ketones by coupling alkyl halides with acid chlorides include activated nickel, prepared by the action of lithium and naphthalene on nickel(II) chloride in glyrae (Vol,8,... 

GOD is immobilized on nanospheres Carboxymethyl CDs are bond through EDC/NHS as coupling agents and EP as cross-linker Acyl chloride linking reaction [59]... 

The Pd-catalyzed coupling of an acyl chloride with benzyl chloride to form the benzyl ketone 854 proceeds in the presence of an excess of Zn. In this reaction, benzyl chloride reacts with Zn to form benzylzinc, which undergoes transmetallation with acylpaliadium complex[729]. The reaction has been applied to the synthesis of riccardin B (855)[730]. 

The acylstannanes 874 and 875 are prepared by the reaction of acyl chlorides with (MciSnl - The symmetrical 1,2-diketones 877 can be prepared by the reaction of an excess of benzoyl chloride with (EtjSn) . Half of the benzoyl chloride is converted into the benzoyltin reagent 876, which is then coupled with the remaining benzoyl chloride under a CO atmosphere to afford the a-diketone 877[748], Triethyl phosphite is used as a ligand. 

Trialkylvinylstannanes undergo cross-coupling reactions with acyl chlorides, as shown by reactions 58307 and 59308. These acylations can be conducted under reductive conditions to saturate the carbon-carbon double bond, as illustrated in reaction 60309. Also... 

Iron-catalyzed cross-coupling reactions of various acyl chlorides or thioesters with Grignard reagents have been pioneered by Marchese et al. and other research groups.322 These transformations provide general and convenient access to a wide range of ketones and have been further extended to the use of a supported iron(lll) complex.323... 

Reactions of Acylzirconocene Chlorides as "Unmasked Acyl Group Donors 5.4.4.5 Cu-catalyzed cross-coupling reactions... 

In the Pd-catalyzed cross-coupling reactions of acylzirconocene chlorides with allylic halides and/or acetates (Section 5.4.4.4), the isolation of the expected p,y-unsaturated ketone is hampered by the formation of the a, P-un saturated ketone, which arises from isomerization of the p,y-double bond. This undesirable formation of the unsaturated ketone can be avoided by the use of a Cu(I) catalyst instead of a Pd catalyst [35], Most Cu(I) salts, with the exception of CuBr - SMe2, can be used as efficient catalysts Thus the reactions of acylzirconocene chlorides with allyl compounds (Table 5 8 and Scheme 5 30) or propargyl halides (Table 5.9) in the presence of a catalytic amount (10 mol%) of Cu(I) in DMF or THF are completed within 1 h at 0°C to give ffie acyl--allyl or acyl-allenyl coupled products, respectively, in good yields. ill... 

Even an oligopeptide has been attached to (Table 4.3, compound 130) [111]. This was achieved by a coupling reaction of the carboxylic group in the side chain of the cyclopropane ring as well. First, the tert-butylcarboxylate 129 was synthesized by the reaction of the corresponding diazomethylbenzoate with Cgg. After hydrolysis with trifluoromethanesulfonic acid, the acyl chloride was generated by treatment with oxalyl chloride. Finally, in a one-step procedure the fullerene peptide 130 was obtained by the reaction with the N-deprotected pentapeptide H-(L-Ala-Aib)2-L-Ala-OMe. 

Malonyl chloride reacted with boiling acetone to give the bicyclic 2 1 adduct 210 comprising a pyranone and a l,3-dioxan-4-one moiety (Scheme 99). The modest yield was compensated for by the ease of its preparation. Compound 210 bears a chloride which is almost as reactive as an acyl chloride and which can be substituted by various nucleophiles in a Stille coupling in modest yields <1997SL895>. Treatment of malonyl chloride with ketene and acetone at low temperature afforded symmetric bis(l,3-dioxin-4-ones) in 60% yield although a different reaction pathway may be assumed (Scheme 99) <2000TL4959>. 

In 1997, Dunn and Jackson reported on a new approach to the synthesis of di- and tripeptides with unnatural amino acids by converting di- and tripeptides into organozinc reagents and coupling them with aryl iodides or acyl chlorides in the presence of Pd2(dba)3 and either PPhs or P(o-tol)3 under mild reaction conditions, with no loss of optical purity. " The synthesis of jS- and y-amino acids in an analogous fashion was reported shortly after (Scheme 12). " ... 

Gansauer, and a titanocene complex, TiCl3(THF)3, is also applicable as disclosed by Nelson and co-workers Catalytic pinacol coupling reactions occur with TiCU and zinc (or aluminum) in the presence of an acylating reagent such as acetic anhydride or acetyl chloride. ... 

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