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Aza-[4 + 2]-cycloaddition of benzocyclobutenones into isoquinolinone derivatives enabled by photoinduced regio-specific C-C bond cleavage.

Nat Commun

December 2024

Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China.

The activation of C-C bond of benzocyclobutenones under mild reaction conditions remains a challenge. We herein report a photoinduced catalyst-free regio-specific C1-C8 bond cleavage of benzocyclobutenones, enabling the generation of versatile ortho-quinoid ketene methides for aza-[4 + 2]-cycloaddition with imines, which offers a facile route to isoquinolinone derivatives, including seven family members of protoberberine alkaloids, gusanlung A, B, D, 8-oxotetrahydroplamatine, tetrahydrothalifendine, tetrahydropalmatine, and xylopinine. Furthermore, the catalytic enantioselective version of this strategy is also realized by merging synergistic photocatalysis and chiral Lewis acid catalysis.

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Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect.

Nat Commun

December 2024

Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, Hangzhou, China.

Natural enzymes feature distinctive second spheres near their active sites, leading to exquisite catalytic reactivity. However, incumbent synthetic strategies offer limited versatility in functionalizing the second spheres of heterogeneous catalysts. Here, we prepare an enzyme-mimetic single Co-N atom catalyst with an elaborately configured pendant amine group in the second sphere via 1,3-dipolar cycloaddition, which switches the oxygen reduction reaction selectivity from the 4e to the 2e pathway under acidic conditions.

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Building a Co-Salen-Immobilized Porous Organic Polymer Catalyst for CO Cycloaddition.

Macromol Rapid Commun

December 2024

Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China.

The CO-epoxide addition to cyclic carbonate is of great significance but usually requires high temperatures and CO pressures. Herein, a spirobifluorene-based porous organic polymer catalyst is designed with a Co-salen complex immobilized on the backbone (ST-CoSalen-POP) to enable CO fixation under mild conditions. ST-CoSalen-POP possesses a high Co-loading content (9.

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Asymmetric Synthesis of Optically Active Pyrazolidines or Pyrazoline Derivatives via Ni(II)-Bipyridine-,'-dioxide Complexes.

Org Lett

December 2024

School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003, China.

Easily obtainable and efficient chiral -symmetric bipyridine-,'-dioxide ligands with Ni(OTf) were developed for application in catalyzing [3 + 2] cycloaddition reactions to synthesize optically active fused pyrazolidines or pyrazoline derivatives featuring three contiguous stereogenic centers by employing azomethine imines and α,β-unsaturated 2-acyl imidazoles, affording the corresponding adducts with the opposite configuration compared to previous synthetic products in 80-98% yields with 28-99% ee and >20:1 dr. In addition, subsequent amplification experiments and derivative transformations of the product further demonstrated the efficient catalytic performance of the catalyst Ni(II)-bipyridine-,'-dioxide complexes and the practicality of this synthesis methodology.

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Among the various studies on CO2 utilization, the sustainable and cost-effective fixation of CO2 into cyclic carbonates remains one of the most intriguing subjects. To this end, a novel type of  composite dicationic ionic liquid material, DIL@PDIL, was developed. This composite consists of a dicationic ionic liquid (DIL), DMAP[TMGH]Br, supported on a polymeric dicationic ionic liquid (PDIL), P-DVB/Im[TMGH]Br.

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