Herein, a base metal-enabled chemodivergent cyclization of propargylamines for the atom-economic construction of nitrogen heterocycles has been developed. Due to the different modes of activation of metal to propargylamine, copper-catalyzed 6 cyclization generates functionalized 2-substitued quinoline-4-carboxylates, while iron-promoted cascade amino Claisen rearrangement, aromatization, and aza-Michael addition afford diverse 2-substituted indole-3-carboxylate derivatives. Excellent selectivity, broad functional group tolerance, mild conditions, and flexible late-stage functionalization illustrate the high efficiency and synthetic utility of this chemodivergent reaction.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.3c03725 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Condition-Controlled Rh(III)-Catalyzed Chemodivergent Cyclization of 2-Arylpyridines with CF-Imidoyl Sulfoxonium Ylides via Triple C-H Activation.
Org Lett
January 2025
Engineering Research Center of Tropical Medicine Innovation and Transformation of Ministry of Education, International Joint Research Center of Human-machine Intelligent Collaborative for Tumor Precision Diagnosis and Treatment of Hainan Province, Hainan Provincial Key Laboratory of Research and Development on Tropical Herbs, School of Pharmacy, Hainan Medical University, Haikou 571199, China.
A condition-controlled Rh(III)-catalyzed selective synthesis of CF-substituted indoles and pyrido[2,1-]isoindoles from 2-arylpyridines and CF-imidoyl sulfoxonium ylides has been developed. The Cp*Rh(MeCN)(SbF)/HFIP system afforded CF-substituted indoles via triple C-H activation, while the [Cp*RhCl]/MeCN condition selectively furnished CF-substituted pyrido[2,1-]isoindoles through C-H [4 + 1] annulation. The notable advantages of this developed method included readily available starting materials, broad substrate scope, and excellent chemoselectivity.
View Article and Find Full Text PDFChemodivergent, enantio- and regioselective couplings of alkynes, aldehydes and silanes enabled by nickel/N-heterocyclic carbene catalysis.
Sci Bull (Beijing)
December 2024
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China. Electronic address:
Divergent synthesis of valuable molecules through common starting materials and metal catalysis represents a longstanding challenge and a significant research goal. We here describe chemodivergent, highly enantio- and regioselective nickel-catalyzed reductive and dehydrogenative coupling reactions of alkynes, aldehydes, and silanes. A single chiral Ni-based catalyst is leveraged to directly prepare three distinct enantioenriched products (silyl-protected trisubstituted chiral allylic alcohols, oxasilacyclopentenes, and silicon-stereogenic oxasilacyclopentenes) in a single chemical operation.
View Article and Find Full Text PDFBase-Promoted Chemodivergent Construction of 2-Chromen-2-one and Chromeno[2,3-]pyrrole Scaffolds from -Quinone Methides and α-Alkylidene Succinimides.
Org Lett
October 2024
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand 247667, India.
Herein, we evolve a base-promoted synthesis of 2-chromen-2-one and chromeno[2,3-]pyrrole scaffolds via (4 + 2) annulation of α-alkylidene succinimides with 2-hydroxyphenyl-substituted -quinone methides (-QMs). Extremely selective and switchable cyclizations were obtained by modifying the base. This metal-free protocol is highlighted by its mild reaction conditions and broad substrate scope, and the viability of the existing protocol was additionally illustrated by gram-scale synthesis and further modification.
View Article and Find Full Text PDFBase-Mediated Chemodivergent [4 + 1] and [2 + 1] Cycloadditions of -Alkylpyridiniums and Enones.
J Org Chem
September 2024
Key Laboratory of Prevention and Treatment of Cardiovascular and Cerebrovascular Diseases, Ministry of Education; Jiangxi Provincal Key Laboratory of Tissue Engineering; School of Pharmaceutical Sciences, Gannan Medical University, Ganzhou 341000, PR China.
Divergent synthesis of structurally different products from the same kinds of starting materials is highly synthetically useful but very challenging. Herein, we reported a base-mediated chemodivergent [4 + 1] and [2 + 1] cycloaddition of -alkylpyridinium and enone under mild conditions, leading to furan-fused bicycles with high diastereoselectivity and spirobicycles, respectively, from moderate to high yields. -Alkylpyridinium salts were modular nucleophilic transfer reagents and C1 synthons, which underwent tandem Michael addition to the α,β-unsaturated ketones and cyclization under the base conditions.
View Article and Find Full Text PDFA solvent controlled regioselective synthesis of 2- and 4-substituted α-carbolines under palladium catalysis.
Chem Commun (Camb)
July 2024
Organic and Medicinal Chemistry Division, CSIR-Indian Institute of Chemical Biology, Kolkata-700032, India.
A facile method for the chemodivergent synthesis of α-carbolines 1 palladium catalyzed [3+3] annulations of tosyliminoindolines 6 with α, β-unsaturated aldehydes 7 is described. Mechanistically, this cascade reaction proceeds through either a -Michael (in DMF) or -Michael (in NMA) pathway followed by intramolecular cyclization of the intermediate. A preliminary photo-physical study on selected products is also reported.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!