RESUMO
A cooperative Rh(II)/Pd(0) dual-catalysis strategy that enabled divergent reactions of α-diazo 1,3-dicarbonyl compounds with allylic carbonates involving ketene versus carbene intermediates is described. The efficient synthesis of α-quaternary allylated ß-keto-esters was accomplished by the Rh(II)/Pd(0) dual-catalysis allylic alkylation of α-diazo 1,3-dicarbonyl compounds. Alternatively, an unprecedented (1+4) annulation of α-diazo 1,3-dicarbonyl compounds with 2-(hydroxymethyl)allyl carbonates via Rh(II)/Pd(0) dual catalysis was also successfully developed, affording a wide variety of α-quaternary tetrahydrofurans in good to high yields.
RESUMO
An efficient and chemoselective transformation of ß-amido ynones to 3-acyl-substituted quinolones 2 and 3-H-quinolones 4 has been developed. In this reaction, ß-cyclic amido ynones can be selectively transformed into quinolones 2 in anhydrous EG via a selective CâO bond cleavage, 1,5-O migration, and CâC bond recombination process. The practical approach of this reaction renders it a viable alternative for the construction of various quinolones.
RESUMO
A Rh(II)-catalyzed oxy-alkynylation of acceptor-acceptor carbenes using EBX reagents was successfully developed. The key alkyne-transfer step is likely to occur through a tandem process involving a ß-addition, an α-elimination, and a 1,2-shift, which was supported by the formation of alkylidene carbene. Various diverse C2-quaternary alkyne-substituted benzofuran-3-ones and 2,2,4,5-tetrasubstituted 3(2H)-furanones can be synthesized smoothly, depending on the choice of diazo compounds and the base additives. Furthermore, this reaction is characterized by mild conditions, high functional group compatibility, and a broad substrate scope.
Assuntos
Alcinos , Compostos Azo , Alcinos/química , Catálise , Compostos Azo/química , Metano/químicaRESUMO
An attractive palladium-catalyzed three-component reaction of ortho-amino aryl diazo esters, allyl carboxylates, and carbon monoxide (CO) has been developed. This catalytic system rendered domino carbene migratory insertion and carbonylation. Remarkably, 2-indolones 3 with a C3 all-carbon quaternary center can be selectively obtained in good to excellent yields via one-pot synthesis, in which two different C-C bonds and one C-N bond were formed in a straightforward manner.
RESUMO
A cooperative Rh(II)/Pd(0) dual-catalysis strategy that promotes a cyclization/allylic alkylation cascade of stable α-diazo-δ-keto-esters has been developed. Highly substituted 3(2H)-furanones with a C2-quaternary center can be obtained efficiently under mild conditions via one-pot synthesis. Remarkably, this binary catalytic system shows high chemo-, regio-, and stereoselectivity and excellent tolerance to various functionalities.
RESUMO
A novel P,N-bidentate ligand-assisted gold-catalyzed oxidative amination of ß-amino-ynones has been developed, allowing the simple and efficient construction of various quaternary ammonium-olate salts in good to excellent yields. These unprecedented quaternary ammonium-olate salts can be isolated and purified via simple suction filtration. The broad substrate scope, easy purification, easy further transformation, and mild conditions make it a viable alternative for the synthesis of various quaternary ammonium-olate salts.
RESUMO
A series of novel pyrazole-benzimidazole derivatives (6-42) have been designed, synthesized and evaluated for their in vitro antiproliferative activity against the HCT116, MCF-7 and Huh-7 cell lines. Among them, compounds 17, 26 and 35 showed significant antiproliferative activity against HCT116 cell lines with the IC50 values of 4.33, 5.15 and 4.84 µM, respectively. Moreover, fluorescent staining studies showed compound 17 could induce cancer cells apoptosis. The flow cytometry assay revealed that compound 17 could induce cell cycle arrest at G0/G1 phase. All in all, these consequences suggest that pyrazole-benzimidazole derivatives could serve as promising compounds for further research to develop novel and highly potent cancer therapy agents.
Assuntos
Antineoplásicos/farmacologia , Benzimidazóis/farmacologia , Desenho de Fármacos , Pirazóis/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Benzimidazóis/química , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Relação Dose-Resposta a Droga , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Estrutura Molecular , Pirazóis/química , Relação Estrutura-AtividadeRESUMO
An unprecedented gold(i)-catalyzed cyclization of cyclopropylidene-tethered propargylic alcohols via a 6-endo-dig enyne cyclization followed by a ring-opening of cyclopropane and nucleophilic closure reaction to construct naphtho[2,3-c]pyrans was developed. This transformation represents a highly efficient method for the synthesis of polycyclic compounds in one-pot, and two new rings are formed in an atom economic manner.
RESUMO
A relay Rh(ii)/Pd(0) dual catalysis that enables domino [1,2]-sigmatropic rearrangement/allylic alkylation of α-diazo tertiary alcohols is described. This transformation represents a highly efficient method for the one-pot synthesis of α-quaternary ß-keto-esters under mild conditions, in which two separate C-C σ-bonds at the carbenic center were formed in a straightforward manner.
RESUMO
A divergent synthesis of Z-iodovinylfurans and 2-acyl furans promoted by NIS via controllable cyclization of ynenones is reported. The reaction proceeded by sequential 5-exo-dig electrophilic cyclization to intermediate 2-(iodomethylene)-2H-furanium cation D, providing a range of synthetically valuable and useful trisubstituted furan derivatives 2 and 3 in moderate to excellent yields. This approach is metal-free, mild, and atom-economic, with good selectivity and high stereoselectivity.
RESUMO
The first gold(III)-catalyzed regioselective oxidation/cycloisomerization of diynes 1 with pyridine N-oxide as the oxidant was developed, providing a range of synthetically valuable and useful fused furan derivatives 3 in moderate to good yields. Control experiments and the confirmation structure of minor products 5 suggest that this chemistry was a concerted gold(III)-catalyzed oxidation/SN2'-type addition/cyclization process via a ß-gold vinyloxypyridinium intermediate and a putative vinyl cation intermediate.
RESUMO
Cyclopropanations of benzene rings by oxidatively generated α-oxo gold carbenes are for the first time demonstrated in a Buchner reaction, in which readily available propargyl benzyl ethers are converted in one-pot to tetrahydropyranone-fused cycloheptatrienes via sequential oxidative gold catalysis and base-promoted isomerization. Additional examples of arene cyclopropanations without fragmentation of the cyclopropane ring are also realized.
RESUMO
A facile gold-catalyzed oxidation terminal alkynes to synthesize substituted dihydronaphthalen-2(1H)-ones 3 and phenanthrenols 5 was realized. Various useful structures and drug precursors were generated in up to 99% yield under mild condition and low catalyst loading.
RESUMO
An efficient two component cycloaddition reaction to synthesize various substituted quinoline derivatives was developed. Ynone 1 was functionalizated by N-oxide attacking the C3-oxetium site and C3-site regioselectively to give 3 and 4. Analogues 3k and 4v have a high binding constant with Hg2+ in CH3CN.
RESUMO
A novel relay Rh(II)/Pd(0) dual catalysis strategy that promotes the divergent reaction of α-diazo-carbonyl compounds with allylic carboxylates for the selective construction of cyclic all-quaternary carbon centers has been developed. This binary catalyst system rendered domino C-H insertion/allylic alkylation process under mild conditions. Remarkably, the domino catalytic reaction shows good selectivity and excellent tolerance to various functionalities and is operationally simple.
RESUMO
An efficient strategy to construct salicyl ketones through gold-catalyzed oxidation/C-H functionalization of ynones is reported. A variety of functionalized salicyl ketones are readily accessed by utilizing this non-diazo approach, thus providing a viable alternative to synthetically useful salicyl ketones with a yield up to 98 %. The α-oxo gold carbenes generated in situ through gold-catalyzed oxidation of ynones can be trapped effectively by internal aryl and heteroaromatic groups. Electronic and steric effects were also investigated in this reaction. The anticancer activity of one salicyl ketone analogue was investigated and its cytotoxicity assays against the PC-3 prostate cancer cell line and SKOV-3 human ovarian carcinoma cell line yield IC50 were 0.81±0.05 and 0.87±0.15â µm, respectively, demonstrating that salicyl ketone analogues showed good anticancer activity.
RESUMO
α-Oxo gold carbenes generated in situ via the gold-catalyzed selective oxidation of 4-oxahepta-1,6-diynes were effectively trapped by internal alkynes, resulting in the formation of 2H-pyran-3(6H)-ones, , and chromen-3(4H)-ones, , upon facile trapping the vinyl cation intermediates by an external N-oxide and internal aryl ring system.
Assuntos
Benzopiranos/síntese química , Di-Inos/química , Ouro/química , Pironas/síntese química , Benzopiranos/análise , Catálise , Compostos Organoáuricos/análise , Compostos Organoáuricos/síntese química , Oxirredução , Pironas/análise , Compostos de Vinila/análise , Compostos de Vinila/síntese químicaRESUMO
A newly developed P,N-bidentate ligand enables enantioselective intramolecular cyclopropanation by a reactive α-oxo gold carbene intermediate generated in situ. The ligand design is based on our previously proposed structure (with a well-organized triscoordinated gold center) of the carbene intermediate in the presence of a P,N-bidentate ligand. A C2-symmetric piperidine ring was incorporated in the ligand as the nitrogen-containing moiety. A range of racemic transformations of α-oxo gold carbene intermediates have been developed recently, and this new class of chiral ligands could enable their modification for asymmetric synthesis, as demonstrated in this study.
Assuntos
Ouro/química , Ligantes , Catálise , Cristalografia por Raios X , Ciclopropanos/química , Metano/análogos & derivados , Metano/química , Conformação Molecular , Nitrogênio/química , Oxirredução , Fósforo/química , Piperidinas/química , EstereoisomerismoRESUMO
Inductive perturbations of C-C triple bonds are shown to dictate the regiochemistry of gold-catalyzed oxidation of internal C-C triple bonds in the cases of propargylic ethers, resulting in highly regioselective formation of ß-alkoxy-α,ß-unsaturated ketones (up to >50/1 selectivity) via α-oxo gold carbene intermediates. Ethers derived from primary propargylic alcohols can be reliably transformed in good yields, and various functional groups are tolerated. With substrates derived from secondary propargylic alcohols, the development of a new P,N-bidentate ligand enables the minimization of competing alkyl group migration to the gold carbene center over the desired hydride migration; the preferred migration of a phenyl group, however, results in efficient formation of a α-phenyl-ß-alkoxy-α,ß-unsaturated ketone. These results further advance the surrogacy of a propargyl moiety to synthetically versatile enone function with reliable and readily predictable regioselectivity.