Intramolecular Copper(I)‐Catalyzed Interrupted Click–Acylation Domino Reaction

Acyl substituted triazoles are valuable scaffolds, but the direct synthesis of these moieties from terminal alkynes by copper catalysis remains unexplored. We report a robust, general, and efficient method using a simple CuI/2,2′‐bipyridine catalytic system. This transformation involves a copper catalyzed azide‐alkyne cycloaddition (CuAAC) followed by an intramolecular acylation onto a carbamoyl chloride. The reaction proceeds under mild conditions, tolerates several functional groups, and is readily scalable. This method represents a novel strategy towards the synthesis of complex heterocycles by a CuAAC/acylation domino process.     

Synthesis and characterization of 7,16-dinicotinoyl- and 7,16-diisonicotinoyltetraaza[14]annulene and their nickel(II) and copper(II) complexes

The reaction of tetraaza[14]annulene and its complexes with nicotinoyl chloride hydrochloride and/or isonicotinoyl chloride hydrochloride produced the 7,16-dinicotinoylated and/or 7,16-diisonicotinoylated corresponding products in satisfactory yields. The mass spectra reveal the molecular ion peaks due to the 7,16-diacylated products. A strong ir band which is correlated with a C = 0 stretching mode is freshly observed in the 1635–1670 cm^?1 region upon the acylation. The electronic spectra for the complexes hardly change upon the acylation, but those for the ligands change slightly. The olefinic proton signals at the 7- and 16-positions disappear on the acylation in ¹H-nmr spectra and the substituted pyridine proton signals are newly observed. The proton nmr results are consistent with those of the carbon-13 nmr. The spin Hamiltonian parameters for the acylated copper(II) complexes are comparable with those for the copper(II) complex which is not acylated. The copper(II) complexes assume the square-planar coordinations with an unpaired electron in the d_x2_?y2 orbital.     

Vinyl copper derivatives 30 reactivity of γ-silylated vinyl copper reagents

γ-silylated vinyl copper reagents react with electrophiles with total retention of configuration of the CC double bond. Oxidation, allylation, vinylation and acylation lead to fonctionalized dienes with a given geometry.     

Synthesis of mono- and di-acylated L-2,6-diamino-4-hexynoic acid potential derivatives for preparation of 3H-labelled lysine containing peptides

The selective acylation of the 6-amino group of 2,6-diamino-4-hexynoic acid was obtained in high overall yield by a simple approach instead of copper complex method.     

Copper ion-induced activation and asymmetric benzoylation of 1,2-diols: kinetic chiral molecular recognition

New catalytic ability of copper(II) ion has been exploited for monobenzoylation of 1,2-diols. The catalyst can be readily modified by ligation to acquire higher stereoselectivity. Highly effective kinetic resolution of dl-1,2-diols was achieved. The enantiodiscrimination process was clearly shown to be controlled by the kinetics of acylation of dl-1,2-diols. The catalytic method was successfully applied to asymmetric desymmetrization of meso-hydrobenzoin.     

3-氧杂多氟戊磺酸催化羧酸的酯化反应及其铜（Ⅱ)盐催化芳烃的Friedel-Crafts酰基化反应

研究使用催化量的3-氧杂多氟戊磺酸催化等摩尔的羧酸和醇的酯化反应和催化 量3-氧杂多氟戊磺酸铜催化芳烃的Friedel-Crafts酰基化反应，并取得较好结果．     

3-氧杂多氟戊磺酸催化羧酸的酯化反应及其铜(II)盐催化芳烃的Friedel-Crafts酰基化反应

研究使用催化量的 3 氧杂多氟戊磺酸催化等摩尔的羧酸和醇的酯化反应和催化量 3 氧杂多氟戊磺酸铜催化芳烃的Friedel Crafts酰基化反应 ,并取得较好结果 .     

(19)F-encoded combinatorial libraries: discovery of selective metal binding and catalytic peptoids

A (19)F NMR method for encoding of combinatorial libraries has been developed. Aryl fluorides whose chemical shifts are modified by aromatic substituents were prepared and attached to resin support beads that were used in the split-pool synthesis of peptoids. The detection of the (19)F NMR signal of tags derived from a single "big bead" was demonstrated. The library diversity arises from peptoid amines and the cyclic anhydrides used in their acylation. The resulting 90-compound library was examined for metal ion binding, and novel ligands for iron and copper were discovered. Their binding constants were determined to be in the low micromolar range using conventional methods. The library was also examined for autocatalysis of acylation, and a molecule possessing the catalytic triad of serine proteases was deduced.     

Synthesis, structure and application of chiral copper(II) coordination polymers for asymmetric acylation

Chiral copper(II) coordination polymers 1a-c have been prepared by one-pot synthesis in high yield. Their single-crystal X-ray analysis showed that repeating units are connected to each other by carboxylate linker and copper(II) atoms are pentacoordinated with distorted square-pyramidal geometry for 1a-b and square-planar geometry for 1c. These polymers have catalyzed the kinetic resolution of secondary alcohols by acylation with up to 90% ee ( s = 50).     

A new method for the synthesis of acyltitanium complexes and their application to copper-mediated acylmetallation of carbon-carbon multiple bonds in aqueous media

Treatment of alpha, beta-unsaturated carbonyl compounds or methyl propargyl ether with acylchlorobis(cyclopentadienyl)titanium in the presence of triethylamine and a copper salt in aqueous THF resulted in acylation of the carbon-carbon multiple bond, yielding the corresponding 1,4-diketones in good yields.     

Synthesis of 4‐Methyl Pyrrolo[2,3‐b]xanthone,a Novel Ring System

A short, high yielding synthesis of a novel substituted pyrrolo[2,3-b]xanthone has been developed. The synthesis begins with a copper catalyzed Ullmann coupling reaction followed by and intramolecular Friedel-Crafts acylation reaction to establish the xanthone core structure. After a regioselective nitration, a Leimgruber-Batcho synthesis establishes the final pyrrole ring.     

Regiospecific Acylation,Alkylation, and Aldol Condensation using magnesium enolates resulting from the conjugate addition of grignard reagents to α, β-unsaturated ketones

The magnesium 3,3-dimethylcyclohex-1-enolate 1i , formed in the copper catalyzed addition of methylmagnesium iodide to 3-methylcyclohex-2-enone, has been subjected to regiospecific electrophilic reactions such as acylation, alkylation, and aldol condensation in order to find a new access to the damascones, ionones and carotenoids. By way of illustration a new synthesis of γ-damascone is described.     

concise synthesis of 4-acylamino analogues of 2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylic acids (LY354740) from an acylnitroso Diels-Alder cycloadduct

Concise total syntheses of 4-acylamino analogues of LY354740 were accomplished employing an N-Boc acylnitroso Diels-Alder cycloadduct as the starting material. The syntheses involved N-O bond cleavage, oxidation, intermolecular cyclopropanation, Bucherer-Bergs reaction, hydrolysis, and regioselective acylation with a temporary copper chelate. The synthesis of an optically active compound was also achieved.     

Synthesis of new metallomesogens based on 3-ketoesters

Ethyl 3-(4-hydroxyphenyl)-3-ketopropionate was synthesized by acylation of acetoacetic ester with 4-acetoxybenzoyl chloride, followed by cleavage of aroylacetoacetic ester and hydrolysis of the protecting acetate group. Further esterification of the phenol hydroxy group with 4-alkoxybenzoic acids resulted in the synthesis of mesogenic 3-aryl-3-keto ester used to produce copper(II) metallomesogenic complexes.     

Cu(II)-catalyzed acylation by thiol esters under neutral conditions: tandem acylation-wittig reaction leading to a one-pot synthesis of butenolides

The first catalytic acylation of alcohols with a thiol ester present in Wittig reagents under neutral conditions catalyzed by the Cu(II) salt through a push-pull mechanism is reported. Furthermore, a new methodology for the one-pot lactonization of acyloins by a copper catalyst is developed. The synthetic utility of this method for the synthesis of natural products is shown.     

Highly Stable Univalent Copper of a Cu@Al/SBA-15 Nanocomposite Catalyzes the Synthesis of Fluorescent Aminobenzotriazoles Derivatives

With the development of green chemistry, it is still a challenge to maintain the unstable valence state of the metal in heterogeneous catalysts and realize new catalytic synthesis methods. In this paper, it is reported that an univalent copper nanocomposite (Cu@Al/SBA-15) can efficiently catalyze the formation of novel amino-containing benzotriazoles with great fluorescence properties in a new synthetic strategy. Subsequently, its application is further verified by an acylation reaction to produce a series of novel benzotriazoles derivatives with high yield. It is worth noting that the Cu@Al/SBA-15 nanocomposites not only enable the reaction completed with high yield in a short time, but can also be recycled many times without a significant reduction in activity, and the leaching of copper and aluminum species in reaction system is negligible. Finally, the detailed and feasible reaction mechanism is also provided.     

Porphyrazines as molecular scaffolds: flexible syntheses of novel multimetallic complexes

Reductive deselenation of selenodiazole-fused porphyrazines, followed by acylation of the resultant labile porphyrazinediamines, was used to prepare macrocycles bearing two Collins ligands, two oxamido residues, or two quinoline-2-carboxamido units. Peripheral coordination of copper(II) to the di-(quinoline-2-carboxamido)-porphyrazine gave a metal-linked face-to-face porphyrazine dimer array. Sequential derivatization of the two amino groups in the porphyrazinediamines was used to prepare mixed peripheral ligand systems including a dimetallic picolinamido-Schiff base porphyrazine. Such systems exhibit strong metal-metal spin coupling and are anticipated to be of value in the synthesis of novel electronic and magnetic materials.     

Macrobicyclic cage amine ligands for copper radiopharmaceuticals: a single bivalent cage amine containing two Lys3-bombesin targeting peptides

The synthesis of new cage amine macrobicyclic ligands with pendent carboxylate functional groups designed for application in copper radiopharmaceuticals is described. Reaction of [Cu((NH(2))(2)sar)](2+) (sar = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) with either succinic or glutaric anhydride results in selective acylation of the primary amine atoms of [Cu((NH(2))(2)sar)](2+) to give derivatives with either one or two aliphatic carboxylate functional groups separated from the cage amine framework by either a four- or five-atom linker. The Cu(II) serves to protect the secondary amine nitrogen atoms from acylation, and can be removed to give the free ligands. The newly appended carboxylate functional groups can be used as sites of attachment for cancer-targeting peptides such as Lys(3)-bombesin. The synthesis of the first dimeric sarcophagine-peptide conjugate, possessing two Lys(3)-bombesin peptides tethered to a single cage amine, is presented. This species has been radiolabeled with copper-64 at ambient temperature and there is minimal dissociation of Cu(II) from the conjugate even after two days of incubation in human serum.     

Rhodium(III)/Copper(II)‐Promoted trans‐Selective Heteroaryl Acyloxylation of Alkynes: Stereodefined Access to trans‐Enol Esters

Enol esters are versatile synthetic building blocks which can be elaborated by a wide variety of transformations. The classical synthesis by O‐selective enolate acylation often hampers control of the E/Z selectivity with highly substituted substrates. A rhodium(III)/copper(II)‐mediated process is reported to provide tetrasubstituted enol esters in a trans‐selective fashion. Overall, the reaction consists of a heteroaryl acyloxylation of alkynes. The process is initiated by a rhodium(III)‐catalyzed C2‐selective activation of electron‐rich heteroarenes, such as benzofuran, furan, and thiophene. Upon addition across an alkyne, a transmetalation to copper(II) enables reductive C? O bond formation. The transformation allows the three‐component couplings of heteroarenes, alkynes, and carboxylic acids. Application of the method in the functionalization of bioactive furocoumarin natural products is also described.     

Novel aurophilic organic ligands based on 1,3-dibromo-propan-2-ol and 2-aminothiophenol

The nucleophilic substitution reactions in 1,3-dibromo-propan-2-ol and the products of its acylation under the action of 2-aminothiophenol were investigated. It was shown that the resulting derivatives containing nitrogen and sulfur donor atoms form coordination compounds in the reactions with copper(II) salts. The possibility of chemosorption of the obtained ligands and complexes containing additional disulfide fragments on the gold electrode surface with the formation of an Au-S bond was demonstrated.