Atom-efficient cross-coupling reactions of triarylbismuths with acyl chlorides under Pd(0) catalysis

The atom-efficient cross-coupling reaction of triarylbismuths with a variety of aliphatic, aromatic, and hetero-aromatic acyl chlorides was demonstrated to afford high yields of cross-coupled ketones under palladium catalysis. The corresponding cross-coupling reaction with diacid chlorides also furnished bis-coupled ketones in good yields.     

A palladium catalyzed atom-efficient cross-coupling reactivity of triarylbismuths with α,β-unsaturated acyl chlorides

An atom-efficient cross-coupling reactivity of triarylbismuths (1 equiv) was demonstrated by cross-coupling reaction with 3 equiv of α,β-unsaturated acyl chlorides under palladium catalysis in the synthesis of a series of functionalized α, β-unsaturated ketones in high isolated yields.     

An atom-efficient palladium-catalyzed cross-coupling reaction of triarylbismuths with acid chlorides: synthesis of diaryl and alkyl aryl ketones

The cross-coupling reaction of triarylbismuths with acid chlorides using a catalytic amount of PdCl₂/PPh₃ afforded the corresponding ketones in high yields. The reactions of aromatic and aliphatic acid chlorides occurred with atom efficiency, as 3 equiv of acid chlorides coupled effectively with 1 equiv of triarylbismuths to yield 3 equiv of the corresponding diaryl and alkyl aryl ketones.     

Pd-catalyzed synthesis of α-aryl ketones through couplings of α-arylacetyl chlorides with triarylbismuths as multi-coupling nucleophiles

The cross-coupling reaction of α-arylacetyl chlorides with triarylbismuths was studied under Pd-catalyzed conditions. The reaction was found to be facile under the established protocol and furnished high yields of α-aryl ketones in short reaction times. This work also demonstrated a facile synthesis of various regio-isomeric mono-, di- and tri-substituted α-aryl ketones in high yields. Triarylbismuths were employed as sub-stoichiometric multi-coupling organometallic nucleophiles in this coupling protocol.     

Pd(0)-catalyzed couplings using bromide and chloride derivatives of Baylis-Hillman adducts with triarylbismuths as atom-efficient multi-coupling nucleophiles

Bromide and chloride derivatives of Baylis-Hillman adducts have been demonstrated to react efficiently with triarylbismuths affording allylic arylated products in high yields under palladium-catalyzed conditions. Triarylbismuths have been employed in sub-stoichiometric amounts as multi-coupling and atom-efficient nucleophiles in these reactions. The reactivity of both allylic bromides and chlorides was found to be facile and equally efficient in couplings with triarylbismuths.     

Room temperature palladium catalysed coupling of acyl chlorides with terminal alkynes

Conditions are reported for the facile, high-yielding coupling of acyl chlorides with terminal alkynes in a reaction involving palladium and copper iodide; the reaction is tolerant of a wide variety of acyl chlorides and terminal alkynes and provides a convenient one-pot route to acetylenic ketones.     

Protocols for amide high-speed analoging. Preparation of novel, small molecule cathepsin D inhibitors

Procedures for solution phase parallel synthesis of new, small molecule cathepsin D inhibitors by the coupling of acyl chlorides, sulfonyl chlorides and carboxylic acids with nitrogen nucleophiles have been established using polymer-bound reagents to facilitate the chemistry and/or to efficiently scavenge the unreacted starting materials and reaction by-products. Silver(I) benzoate was used to facilitate the coupling of acyl chlorides with less reactive anilines. Compound 4 was identified as a sub-micromolar cathepsin D inhibitor (IC₅₀=320 nM).     

Arylations of allylic acetates with triarylbismuths as atom-efficient multi-coupling reagents under palladium catalysis

Arylation of allylic acetates employing triarylbismuths as multi-coupling reagents under palladium-catalyzed conditions was reported. Triarylbismuths as nucleophilic coupling partners were used in sub-stoichiometric amounts with respect to allylic acetates and thus served as atom-efficient multi-coupling reagents. A variety of allylic acetates were cross-coupled with triarylbismuths to furnish the corresponding functionalized 1,3-disubstituted propenes in good to excellent yields in short reaction times. The reported palladium protocol also yielded chemo-selective allylic arylations in high yields.     

Visible-Light Photoredox-Catalyzed Acyl Lactonization of Alkenes with Acyl Chlorides

A photocatalytic acyl lactonization of unsaturated carboxylic acids using simple and inexpensive acyl chlorides has been developed for a modular synthesis of acyl lactones. Significantly, the simple protocol could allow an efficient construction of biologically important phthalide framework. The transformation could be extended to a wide variety of unsaturated carboxylic acids, including substituted 2-vinyl benzoic acids and different types of alkenoic acids. Moreover, a series of aroyl, heteroaroyl chlorides could serve as coupling partners. Notably, functional groups including MeO, F, Cl and Br could survive. It is believed that acyl radicals generated from acyl chlorides under photoredox catalysis reacted with alkenes via atom-transfer radical addition (ATRA) and triggered subsequent lactonization in the process. Preliminary mechanistic investigations revealed that the transformation probably proceeded through a free radical pathway.     

Synthesis of Ketones from Acyl Chlorides and Triorganoindium Reagents by Pd‐Catalyzed Cross‐Coupling

Triorganoindium reagents prepared from indium tribromide and 3 equiv of organolithium reagents react with acyl chlorides in palladium‐catalyzed cross‐coupling for preparation of new ketones.     

A versatile access to unsymmetrical and symmetrical α-diketones via organotin reagents

Unsymmetrical α -diketones have been obtained via cross coupling of acyltins with acyl halides under PdCl₂(PPh₃)₂ catalysis while symmetrical α -diketones have been readily obtained via “in situ” formation of acyltins using hexabutylditin and acyl chlorides under similar experimental conditions.     

An improved method of amide synthesis using acyl chlorides

A simple, mild and highly efficient condition for amide synthesis from acyl chlorides has been developed to minimize hydrolysis, racemization and other side reactions. This method should expand capabilities in the peptide coupling area.     

One-Pot Stereoselective Synthesis of (Z)-α-Arylthio-α,β-unsaturated Ketones by Hydrostannylation–Stille Tandem Reaction of Acetylenic Sulfides

(Z)-α-Arylthio-α,β-unsaturated ketones can be stereoselectively synthesized in one pot under mild conditions, in good yields, by the palladium-catalyzed hydrostannylation of acetylenic sulfides with tributyltin hydride, followed by Stille coupling with acyl chlorides.     

Microwave-assisted, boron trichloride mediated acylation of phenols-synthesis of (o-hydroxyaryl)(aryl)methanones and xanthones

A novel and efficient microwave-assisted, BCl(3) mediated coupling reaction to synthesize o-(hydroxyaryl)(aryl)methanone structures from phenols and acyl chlorides is described. This reaction was further incorporated into a two-step synthesis of biologically interesting xanthones.     

Using Pd-salen complex as an efficient catalyst for the copper-and solvent-free coupling of acyl chlorides with terminal alkynes under aerobic conditions

<正>The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base,giving excellent ynones under aerobic conditions.     

Indium-mediated mild and facile method for the synthesis of amides

Indium-mediated coupling reactions of acyl chlorides and amines for the synthesis of amide bonds are described. The reaction afforded high yields of the desired amides under mild and neutral conditions, and it was applicable also to the preparation of peptides without epimerization.     

Palladium‐ and Solvent‐Free Synthesis of Ynones by Copper(I)‐Catalyzed Acylation of Terminal Alkynes with Acyl Chlorides under Aerobic Conditions

Air‐stable Cu^I/cryptand‐22 complex was found to be a highly active catalyst for the solvent‐free cross‐coupling reaction of terminal alkynes with different acyl chlorides in the presence of Et₃N as base to give the corresponding ynones in quantitative yields.     

Acylation des β-énaminoesters: Regio et stéréoformation des β-énaminoesters N- ou C-acylés

The reaction of acyl chlorides with cyclic five-membered β-enaminoesters gave exclusively N-acylated products while reaction of acyl chlorides with cyclic seven-membered β-enaminoesters gave only C-acylated products. In the case of cyclic six-membered β-enaminoesters, the reaction of acyl chlorides gave a mixture of N-acylated and C-acylated products.     

铜催化下格氏试剂与酰卤的选择性偶合: 直链酮化合物的合成

在一般情况下,格氏试剂与酰卤偶合反应难以控制在酮阶段,往往得到叔醇。在较低温度下有机铜试剂与酰卤偶合可高产率地得到酮,所以用固体铜盐CuX(X=Cl、Br、I)作为格氏试剂与酰卤偶合的催化剂,可以提高反应的选择性,从而提高酮的产率。但固体铜盐的催化反应仅适合于空间位阻较大的脂肪酮和某些芳香酮的制备,对于直链脂肪酮的制备则产率很低。我们采用可溶性铜络合物Li_2Cucl_4(四氯合铜酸锂)等作催化剂,在均相溶液中反应,有效地提高了催化效果及反应的选择性,从而使格氏试剂与酰卤的偶合反应成功地用于直链脂肪酮的制备,产率良好。     

A comparative study of the reactions of fluorinated oxi- and thiiranes with acyl chlorides

The CoCl₂-catalyzed reactions of fluorinated 1,2-oxi- and thiiranes with acyl chlorides were studied. It was found that a regioselective heterocycle opening reaction resulted in two isomers having normal and abnormal structure in a ratio predetermined by the substituents in both the starting heterocycles and acyl chlorides.