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Herein, a gold-catalyzed alkyne oxidative cyclization/Mannich-type addition cascade reaction of ynamides with 1,3,5-triazinanes in the presence of a Brønsted acid has been presented. A class of functionalized fluorenes bearing a quaternary carbon center was synthesized directly with moderate to excellent yields via in situ formed α-oxo carbenes using quinoline N-oxide as the oxidant under mild reaction conditions.
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Enantioselective construction of all-carbon quaternary stereocenters has attracted much attention over the past few decades. A variety of catalytic asymmetric methods have been disclosed based on the use of presynthesized complex reagents that impart congested steric hindrance to the reaction center, which generally produce the chiral molecules through forming one C-C bond. The use of readily available reagents that could build two C-C bonds on the same carbonic center with the concomitant assembly of quaternary stereocenters remains challenging. Herein, we disclose a catalytic asymmetric alkyne multifunctionalization reaction using a gold complex and a chiral spiro phosphoric acid (SPA) for synergistic catalysis. In this method, the readily accessible internal alkynes served as the key gold carbene precursors, followed by carbene gem-dialkylation through Mannich-type addition of enolate species or stepwise formal cycloaddition with methylenimines that are derived from 1,3,5-triazinanes in the presence of SPA. The reaction provides practical access to poly-functionalized chiral linear and cyclic ketones that bear two adjacent quaternary stereocenters in generally good yields and excellent enantioselectivities, leading to an essential complement to the asymmetric construction of quaternary stereocenters using readily available materials with high bond formation efficiency.
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A robust and practical difluoroalkylation synthon, α,α-difluoroenol species, which generated in situ from trifluoromethyl diazo compounds and water in the presence of dirhodium complex, is disclosed. As compared to the presynthesized difluoroenoxysilane and in situ formed difluoroenolate under basic conditions, this difluoroenol intermediate displayed versatile reactivity, resulting in dramatically improved enantioselectivity under mild conditions. As demonstrated in catalytic asymmetric aldol reaction and Mannich reactions with ketones or imines in the presence of chiral organocatalysts, quinine-derived urea, and chiral phosphoric acid (CPA), respectively, this relay catalysis strategy provides an effective platform for applying asymmetric fluorination chemistry. Moreover, this method features a novel 1,2-difunctionalization process via installation of a carbonyl motif and an alkyl group on two vicinal carbons, which is a complementary protocol to the metal carbene gem-difunctionalization reaction.
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Asymmetric catalytic carbene reactions have been well documented in the last few decades for the expeditious assembly of chiral molecules with structural diversity. However, the enantioselective construction of all-carbon quaternary centers remains a challenge in this area. In this review article, two types of asymmetric carbene reactions that beyond cyclopropanation, cyclopropenation, and Büchner reaction, have been summarized for the construction of all-carbon quaternary centers: 1) using carbene species as a 1C synthon that reacts with a trisubstituted prochiral center; 2) sequential installation of two different C-C bonds on the carbene position, which features a gem-difunctionalization reaction. Especially, the asymmetric metal carbene gem-dialkylation process, which has emerged as a practical and versatile method for the expeditious assembly of complex architectures from readily available chemical resources, is a complementary approach for the expeditious assembly of all-carbon quaternary centers.
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Cyclobutanone is a strained motif with broad applications, while direct assembly of the aromatic ring fused cyclobutanones beyond benzocyclobutenone (BCB) skeletons remains challenging. Herein, we report a Rh-catalyzed formal [3+2] annulation of diazo group tethered alkynes involving a 4-exo-dig carbocyclization process, providing a straightforward access to furan-fused cyclobutanones. DFT calculations disclose that, by comparison to the competitive 5-endo-dig process, 4-exo-dig carbocyclization is mainly due to lower angle strain of the key sp-hybridized vinyl cationic transition state in the cyclization step. Using less reactive catalysts Rh2(carboxylate)4 is critical for high selectivity, which is explained as catalyst-substrate hydrogen bonding interaction. This method is proved successful to direct access previously inaccessible and unknown furan-fused cyclobutanone scaffolds, which can participate in a variety of post-functionalization reactions as versatile synthetic blocks. In addition, preliminary antitumor activity study of these products indicates that some molecules exhibite significant anticancer potency against different human cancer cell lines.
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A novel and highly stereoselective acyclic 1,3-difunctionalization of vinyl metal carbene species has been developed via Rh(II)/chiral phosphoric acid co-catalyzed three-component reactions of vinyldiazoacetates with alcohols and imines. This innovative approach features excellent regio-, diastereo-, and enantioselectivities, demonstrating a broad scope and functional group compatibility. Notably, this is the first example of three-component asymmetric acyclic 1,3-difunctionalization with in situ-formed vinyl metal carbenes.
RESUMEN
The catalytic asymmetric construction of all-carbon quaternary stereocenters has received tremendous interest over the past decades, and numerous efficient protocols have been disclosed based on the formation of one C-C bond between two assembling reactants. However, the use of asymmetric multi-component reactions that build two C-C bonds on the same carbonic center with concomitant assembly of quaternary stereocenters is rare and remains challenging. Herein, we disclose an enantioselective three-component reaction of α-diazo ketones with alkenes and 1,3,5-triazines under dirhodium/chiral phosphoric acid cooperative catalysis, which leads to a practical and atom-economic synthesis of poly-functionalized chiral ketones that bear a α-quaternary stereocenter in generally good to high yields with excellent enantioselectivities. In comparison to the previous method for the construction of tertiary and quaternary stereocenters via carbene gem-difunctionalization reactions, this reaction features an unprecedented gem-dialkylation process via sequential installation of two C-C bonds on the carbene center in one reaction, providing an essential complement to the asymmetric construction of all-carbon quaternary stereocenters using common and readily available starting materials.
Asunto(s)
Carbono , Metales , Estructura Molecular , Carbono/química , Estereoisomerismo , Cetonas/químicaRESUMEN
Coral concrete has low cost and convenient materials, making it an excellent raw material for processing. However, its lower strength limits the application of coral concrete. Surface modification is expected to increase the properties of porous coral concrete. In this study, single and compound modification treatments were applied to the surface of a coral aggregate to improve its properties for promoting the mechanical performance of coral concrete. The results showed that the micro-aggregate effect and pozzolanic activity of granulated blast furnace slag (GBFS) and the permeability and polycondensation of sodium silicate (SS) could be mutually promoted. The GBFS and SS could effectively fill the pores of the coral aggregate, enhancing the properties of the aggregate, such as density and load-bearing capacity, and reducing the water absorption and crushing index by more than 50%. GBFS and SS could intensify and accelerate the hydration of cement, and generate a large number of hard hydration products at the interfacial transition zone (ITZ), which could strengthen the bonding between the aggregate and mortar, improving the strength of the ITZ. The compressive strength of the coral concrete was significantly increased.
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Silane coupling agent (SCA), a kind of organic solvent, was introduced to improve the performance of coral coarse aggregates and enhance the interfacial adhesion between the inorganic coral aggregate and the cement paste of coral concrete. The crushing indicator and water absorption of the coral aggregates over various dipping times were measured, and the slump, interface microhardness, and compressive strength of coral concrete tested. The microscopic appearances of the coral concrete before and after modification were analyzed based on SEM images. The experimental results indicate that SCA can effectively reduce the crushing indicator and water absorption of coral coarse aggregates, and the modification performance becomes better over time. SCA facilitates the generation of chemical forces between the coral aggregates and cement mortars, improves adhesion between the aggregates and mortars, augments the microhardness of the interface, and increases the compressive strength. According to the microscopic appearance of the treated and untreated coral aggregate interfaces, the aggregates and the mortars are in closer combination after modification.
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An efficient gold and chiral phosphoric acid cooperatively catalyzed enantioselective oxidative cyclization/Mannich-type addition reaction of homopropargyl amides with nitrones has been developed, which provides chiral pyrrolidin-3-ones in high yields with excellent enantioselectivities under mild conditions. This reaction employed stable and readily available alkynes as non-diazo carbene precursors, which provides a 100% atom economy method with high bond formation efficiency.
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In this paper, an ultrahigh-strength marine concrete containing coral aggregates is developed. Concrete fabricated from marine sources is considered an effective and economical alternative for marine engineering and the construction of remote islands. To protect sea coral ecosystems, the coral aggregates used for construction are only efflorescent coral debris. To achieve the expected mechanical performance from the studied concrete, an optimal mixture design is conducted to determine the optimal proportions of components, in order to optimize the compressive strength. The mechanical properties and the autogenous shrinkage, as well as the heat flow of early hydration reactions, are measured. The hydration products fill up the pores of coral aggregates, endowing our concrete with flowability and self-compacting ability. The phases in the marine concrete are identified via X-ray diffraction analysis. The 28-day compressive and flexural strength of the developed marine concrete achieve 116.76 MPa and 18.24 MPa, respectively. On account of the lower cement content and the internal curing provided by coral aggregates, the volume change resulting from autogenous shrinkage is only 63.11% of that of ordinary reactive powder concrete.
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An unprecedented desaturation method via redox-neutral hydrogen transfer process has been disclosed under mild conditions for the selective formation of terminal alkene with alkyl diazo compounds and aza-o-QMs. The control experiments and DFT calculations suggest that the visible light was introduced as a key parameter to enhance the reactivity via a radical process in the formation of closed-shell cyclopropane intermediate, followed by a ring opening and redox-neutral hydrogen transfer process to give the desaturated product. The high regioselectivity in this transformation is enabled by the internal amino species as an ancillary group (AG) in the final olefin formation step. This method provides a missing link in the expeditious preparation of synthetically useful 2-allyl anilines with broad substrate generality. Further applications of these generated products in N-heterocycle construction, including 5- and 6-membered rings with structural diversity, have been tactfully explored, which highlight the potential in methodology development and drug discovery.
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A copper-catalyzed formal [1 + 2 + 2]-annulation of alkyne-tethered diazo compounds with pyridines, which affords polycyclic fused indolizines in synthetically useful to good yields under mild reaction conditions, has been reported. This method features the use of an inexpensive copper catalyst and readily available starting materials, broad substrate generality, and operational simplicity. Notably, a variety of natural product derivatives are compatible under the current conditions, which shows significant potential of this method for the selective decoration and modification of analogous biomolecules or pharmaceuticals.
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A gold-catalyzed 6-endo-dig carbocyclization of alkyne with the pendent diazo group is reported. It provides an expeditious approach for the synthesis of multi-functionalized naphthalene derivatives under mild conditions. Mechanistic studies suggest that a vinyl gold carbene is generated as the key intermediate in this cascade transformation that smoothly delivers naphthalene products through an unprecedented stepwise aromatization or an intermolecular aromatic substitution process. The unique endocyclic vinyl species is inaccessible with other precursors; thus, novel carbene cascade transformations could be envisioned with the current catalytic model. Functional groups, such as alkenyl, hydroxyl, amino, and carboxyl groups, remain untouched under these conditions. In addition, the utility of these generated 2-carboxyl naphthalenes is illustrated by the synthesis of chiral 1,2'-binaphthalene ligands and π-conjugated polycyclic hydrocarbons (CPHs).
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In the present research work, the effect of extrusion temperature from 480 to 560 °C on the microstructure and mechanical behavior of the SiCnw/2024Al composite (15 vol.%) has been explored. It has been found that extrusion at higher temperature (above 520 °C) was beneficial for the densification of the composite, while the residual average length and alignment of the SiC nanowires were also increased with the extrusion temperature. Moreover, higher extrusion temperature was helpful for the mechanical strength of the SiCnw/2024Al composite, and the peak-aged SiCnw/2024Al composite extruded at 560 °C revealed the highest strength (709.4 MPa) and elastic modulus (109.8 GPa).
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An unprecedented transition-metal-free tandem bicyclization of diaryl alkynes has been disclosed, which provides a streamlined access to a range of polycyclic 2 H-indazoles in high to excellent yields. The salient features of this reaction include readily available starting materials, good functional group compatibility, mild reaction conditions, no column chromatography, high bond-formation efficiency, and ease in further transformations. Notably, this is the first example for the synthesis of 2 H-indazoles with in situ generated diazonium salt as the nitrogen source, and a mechanistic rationale involving an acid-promoted tandem diazonium salt formation/bicyclization process is discussed.
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A thermally induced, substrate-dependent reaction of alkynyl diazo compounds has been developed. This transformation produces spiro-4H-pyrazole-oxindoles and fused 1H-pyrazoles in good to high yields from the corresponding alpha-cyano and alpha-sulfonyl diazo compounds. The salient features of this reaction include excellent chemoselectivity and atom-economy, mild reaction conditions, simple purification and potential for large scale production.
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An unprecedented divergent outcome transformation of alkyne tethered N-sulfonyl hydrazones is reported, which provides a direct and effective access to 4-methyl 2H-chromene derivatives and spiro-4H-pyrazoles in the presence of copper catalyst or under thermal conditions, respectively. The notable features of this process include readily available starting materials, an inexpensive copper catalyst, mild reaction conditions, broad substrate scope, diverse transformations and potential applications of these generated products. Mechanistic studies indicate that the 3H-pyrazole, which is generated via direct [3+2] cycloaddition, is the communal key intermediate of these two divergent transformations. To the best of our knowledge, this is the only example of sulfonation reaction that goes through a cascade process involving 3H-pyrazole, which was isolated and confirmed by single crystal X-ray diffraction analysis for the first time.
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Jiang et al (2004 J. Phys.: Condens. Matter 16 521) present a model based on the traditional broken-bond model for predicting surface energies of elemental crystals. It is found that bias errors can be produced in calculating the coordination numbers of surface atoms, especially in the prediction of high-Miller-index surface energies.