Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
A facile synthetic method for 4-aryl-4,5-dihydropyrrole-3-carboxylates is developed, with a rhodium-catalyzed ring expansion strategy from readily available 2-(azetidin-3-ylidene) acetates and aryl boronic acids. Mechanistic investigations suggest a novel domino "conjugate addition/N-directed α-C(sp)-H activation" process. The asymmetric catalytic synthesis of the 4-aryl-4,5-dihydropyrrole-3-carboxylate is realized by using QuinoxP* (91-97% ee). The synthetic utility of this protocol is demonstrated by the synthesis of 3,4-disubstituted or 2,3,4-trisubstituted pyrrolidines with excellent diastereoselectivities.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.2c00056 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Indole-Quinoline Transmutation Enabled by a Formal Rhodium Carbynoid.
Angew Chem Int Ed Engl
June 2025
Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals, School of Pharmacy, Zunyi Medical University, No. 6 West Xuefu Rd., Zunyi, 563006, China.
Skeleton editing is an emerging and powerful tool in organic chemistry because it can simplify synthetic procedures towards complex molecules. Herein, we present an approach for indole-quinoline transmutation through rhodium-catalyzed single-carbon insertion into the C2(sp)─C3(sp) bond of an indole with an α-diazotrifluoroethyl sulfonium salt that we developed. This protocol involves a formal trifluoromethyl rhodium carbynoid (CFC = Rh) resembling a trifluoromethyl cationic carbyne (CFC:), allowing facile access to an array of quinolines in moderate to high yields.
View Article and Find Full Text PDFRhodium-Catalyzed 1,5-Sigma Migratory Ring Expansion of gem-Difluorodienyl Cyclopropanes and Cyclobutanes.
Angew Chem Int Ed Engl
July 2025
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Rhodium-catalyzed 1,5-sigma migratory ring expansion (SMRE) of common dieneylcyclopropanes (DECPs) and dieneylcyclobutanes (DECBs) fails. But replacing the terminal CH group with CF group for both DECPs and DECBs, the resulting substrates of gem-difluorodienyl cyclopropanes (df-DECPs) and gem-difluorodienyl cyclobutanes (df-DECBs) can achieve this reaction, which has broad reaction scope and high efficiency to give seven- and eight-membered carbocycles with a carbonyl group. The keys to the success of this reaction are: oxidative cyclometalation becomes easier with the help of two F atoms; the metallacycle intermediate can detour the sluggish reductive elimination by defluorination to generate Rh carbene intermediate (defluorocarbenation process), which can undergo easier carbene migratory insertion and β-H elimination, giving rise to the final products.
View Article and Find Full Text PDFRhodium-Catalyzed Atroposelective Synthesis of Axially Chiral 1-Aryl Isoquinolines via De Novo Isoquinoline Formation.
Angew Chem Int Ed Engl
June 2025
New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
Axially chiral heterobiaryl moieties serve as core skeletons for bioactive molecules, chiral ligands, and organocatalysts. Enantioselective de novo formation of the heteroaromatic ring is one of the most straightforward approaches to access enantioenriched heterobiaryls. Herein, an enantioselective de novo construction of isoquinolines by rhodium-catalyzed C─H activation/annulation of aromatic imines with alkynes is disclosed.
View Article and Find Full Text PDFVinylcyclopropanes as Three-Carbon Synthons in Rhodium-Catalyzed Cycloadditions: Reaction Development, Mechanistic Studies, New Inspirations, and Synthetic Applications.
Acc Chem Res
April 2025
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
ConspectusCyclic structures are common in natural products and pharmaceuticals, but pose major synthetic challenges. Transition metal-catalyzed cycloadditions provide a direct and efficient route to complex ring systems in a single step. The demand for new transition metal-catalyzed cycloadditions remains high, as these methods enable access to diverse ring systems with unique substituents and stereochemistries that are often unattainable through existing cycloaddition techniques.
View Article and Find Full Text PDFTunable Synthesis of 4-Acyl- and 4-Formyl Pyrroles by Rhodium-Catalyzed Ring-Expansion of Azirines with Enaminones.
Org Lett
February 2025
National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Province Key Laboratory of Natural and Biomimetic Drugs Research, College of Chemistry and Materials, Jiangxi Normal University, Nanchang, Jiangxi 330022, China.
A rhodium-catalyzed annulation of 2-azirines with enaminones is presented. This protocol affords a convenient approach to the diversity-oriented synthesis of 4-acyl- and 4-formyl pyrroles with good functional group tolerance. The utility of this reaction has been demonstrated by scale-up preparation, late-stage modification of natural molecules, and synthesis of diverse derivatives.
View Article and Find Full Text PDF