RESUMEN
A Pd-catalyzed dual C-H carbonylation of commercially available diarylamines using Co2(CO)8 as a safe CO source has been developed. This methodology provides a facile approach for the synthesis of diversified acridones in moderate to good yields. The protocol features good functional group compatibility, operational safety, easy scale-up, and versatile transformations.
RESUMEN
A copper-catalyzed syn-hydrocarbonization of internal alkynes with N,N-dimethylformamide dimethylacetal and silanes has been disclosed that offers an efficient and expedient access to (E)-α,ß-unsaturated aldehydes. This highly selective process, which can be performed at gram-scale, enjoys operational simplicity, as well as syngas-free conditions.
RESUMEN
A palladium-catalyzed dearomatization of indoles with alkynes has been developed, providing an efficient route to access a variety of synthetically useful spirocyclohexaneindolenines in moderate to good yields. The current method features a simple catalytic system, operational simplicity, and good functional group compatibility, which will contribute substantially to the development of dearomatization to access spiro compounds. Besides, the ubiquitous existence of spiro molecules, including spirocyclohexaneindolenines, in drugs and biological active molecules suggests the potential application of this methodology in medicinal chemistry.
RESUMEN
A novel and facile approach to synthesize arylazopyrroline scaffolds via metal-free cascade reactions of aziridines with arylalkynes and aryldiazoniums has been developed, providing access to a variety of 4-arylazo-2-pyrrolines in a highly concise fashion. This efficient process, which can be performed at the gram scale, enjoys operational simplicity and mild and metal-free conditions.
RESUMEN
Visible-light-initiated homogeneous oxidative synthesis of nitriles from amines was accomplished through a combined use of photoredox and copper catalysis. This transformation was performed at room temperature with O2 as the oxidant.
RESUMEN
The gold-catalyzed enantioselective hydroazidation and hydroamination reactions of allenes are presented herein. ADC gold(I) catalysts derived from BINAM were critical for achieving high levels of enantioselectivity in both transformations. The sense of enantioinduction is reversed for the two different nucleophiles, allowing access to both enantiomers of the corresponding allylic amines using the same catalyst enantiomer.
Asunto(s)
Alcadienos/química , Complejos de Coordinación/química , Oro/química , Aminas/química , Catálisis , Metano/análogos & derivados , Metano/química , EstereoisomerismoRESUMEN
Macrocyclic thermally activated delayed fluorescence (TADF) emitters have been demonstrated to realize high efficiency OLEDs, but the design concept was still confined to rigid π-conjugated structures. In this work, two macrocyclic TADF emitters, Cy-BNFu and CyEn-BNFu, with a flexible alkyl chain as a linker and bulky aromatic hydrocarbon wrapping units were designed and synthesized. The detailed photophysical analysis demonstrates that the flexible linker significantly enhances the solution-processibility and flexibility of the parent TADF core without sacrificing the radiative transition and high PLQY. Moreover, benefiting from sufficient encapsulation of both horizontal and vertical space, the macrocyclic CyEn-BNFu further isolated the TADF core and inhibited the aggregation caused quenching, which benefits the utilization of triplet excitons. As a result, the non-doped solution-processed OLEDs based on CyEn-BNFu exhibit high maximum external quantum efficiencies (EQE) up to 32.3%, which were 3 times higher than those of the devices based on the parent molecule. In particular, these macrocyclic TADF emitters ensure the fabrication of flexible OLEDs with higher brightness, color purity and bending resistance. This work opens a way to construct macrocyclic TADF emitters with a flexible alkyl chain linker and highlights the benefits of such encapsulated macrocycles for optimizing the performance of flexible solution-processed devices.
RESUMEN
Copper-catalyzed direct conversion of benzylic alcohols to aryl nitriles was realized using NH3(aq.) as the nitrogen source, O2 as the oxidant and TEMPO as the co-catalyst. Furthermore, copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved.
Asunto(s)
Amoníaco/química , Alcoholes Bencílicos/química , Cobre/química , Nitratos/química , Nitrilos/síntesis química , Catálisis , Estructura Molecular , Nitrilos/química , Oxidación-Reducción , Agua/químicaRESUMEN
A new, simplified method for the synthesis of dimethyl aryl acylsulfonium salts has been developed. A series of dimethyl aryl acylsulfonium bromides were prepared by the reaction of aryl methyl ketones with hydrobromic acid and dimethylsulfoxide (DMSO). This sulfonium salt confirms that bromine production and the bromination reaction take place in the DMSO-HBr oxidation system. What's more, it is also a key intermediate for the synthesis of arylglyoxals.
Asunto(s)
Bromuros/química , Cetonas/química , Bromuros/síntesis química , Dimetilsulfóxido/químicaRESUMEN
A Pd-catalyzed carbonylative dearomatization via an acyl Pd complex has been developed. Diversified carbonyl-containing spirocyclic indolenines with an all-carbon quaternary center were constructed in an efficient and straightforward way with good to excellent yields. The protocol features a simple catalytic system, operational simplicity, a broad substrate scope, easy scale-up, and versatile transformations. In addition, the asymmetric reaction was initially explored with moderate enantioselectivity.
RESUMEN
A general and expedient method to construct the scaffolds of 2-alkenylpyridines, through copper-catalyzed C2 alkenylation of pyridine-N-oxides with alkynes, has been disclosed. This protocol shows operational simplicity, good functional group compatibility and broad substrate scope.
RESUMEN
A copper-catalyzed borylaminomethylation of multiple carbon-carbon bonds with N,O-acetal and bis(pinacolato)diboron has been disclosed that offers efficient and expedient access to γ-amino boronates. The products contain a valuable amine and boronate, which are amenable to further elaboration, and have versatile synthetic utilities.
RESUMEN
A copper-catalyzed borylative amidation of vinyl arenes with isocyanates and bis(pinacolato)diboron has been developed. This new protocol, which can be performed on a gram-scale, utilizes isocyanates as simple precursors to provide access to a range of boryl alkyl amides. The products contain valuable amide and boronate, which are amenable for further elaboration, and have versatile synthetic utilities.
RESUMEN
N,N-Dimethyl-beta-alanine was found to be a more powerful phosphine-free ligand than the previously reported ligand, N,N-dimethylglycine, in the Pd-catalyzed Heck reaction for a variety of aryl bromides, aryl iodides, and activated aryl chlorides with a practical turnover number of 10(3). Both kinetic and theoretical studies suggested that N,N-dimethyl-beta-alanine led to faster oxidative addition of an aryl halide to Pd than N,N-dimethylglycine. [reaction: see text]