Advances in the Synthesis of Isoquinolines Using an Alkyne Coupling Partner via Transition‐Metal‐Catalyzed C─H Activation

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(2)

Published: Jan. 1, 2025

Abstract Isoquinoline is a privileged structural motif and has extensive applications in asymmetric catalysis, photochemistry, pharmaceutical use. Naturally, isoquinoline popular synthetic target for many research groups worldwide, who, as result, have developed numerous methodologies to afford wide variety of derivatives. The synthesis recent years flourished, employing C─H activation strategies using various transition metal catalysts: rhodium (Rh), ruthenium (Ru), nickel (Ni), manganese (Mn), cobalt (Co). To summarize this diverse area study, review comprehensively assimilates the literature where isoquinolines are synthesized alkynes (both internal terminal) coupling partners. Wherever possible, mechanistic details associated with reported reactions provided.

Language: Английский

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Dearomative Alkylation of Heteroarenium Salts via Blue Light Enabled Homolytic C–C Bond Cleavage

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Alkyl substituted nitrogen heterocycles are important building blocks in drug molecules, agrochemicals, and materials. Herein we report a simple efficient way to prepare such compounds by coupling alkyl halides with heteroarenium salts. Detailed experimental computational studies indicate that this reaction goes through radical avoids the formation of undesired homocoupling salts via recycling dimers C–C bond cleavage under blue light.

Language: Английский

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A shorter and alternative route to duvelisib: application in scale-up synthesis

Journal of the Indian Chemical Society, Journal Year: 2025, Volume and Issue: unknown, P. 101713 - 101713

Published: April 1, 2025

Language: Английский

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Palladium‐Catalyzed [3+2+1]/[4+2] Heteroannulation of Allylamines with CO and 1,4‐Enynes Leading to 1,7,8,8a‐Tetrahydroisoquinolin‐3(2H)‐ones

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Comprehensive Summary Aminocarbonylative heteroannulation of unsaturated hydrocarbons with amines and CO has become a key transformation in organic synthesis to build N ‐heterocycles. In this report, new palladium‐catalyzed aminocarbonylative [3+2+1]/[4+2] allylamines 4‐en‐1‐yn‐3‐yl acetates for the 1,7,8,8a‐tetrahydroisoquinolin‐3(2 H )‐ones been developed. The method enables construction two six‐membered rings single reaction step leading formation isoquinolinone scaffolds, featuring excellent selectivity, good functional group compatibility broad substrate scope. A possible mechanism involving Pd‐catalyzed isomerization form allenyl‐Pd intermediate, aminocarbonylation cycloaddition was proposed.

Language: Английский

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Mechanistic Studies on Rh(III)-Catalyzed Defluorinative Annulation of N-Sulfonylarylamides with Ethyl 2-Diazo-3,3,3-Trifluoropropanoates

Organometallics, Journal Year: 2024, Volume and Issue: 43(17), P. 1861 - 1868

Published: Aug. 12, 2024

The synthesis of fluorinated isoquinoline derivatives holds significant value in organic and medicine. Research into the reaction mechanisms possible pathways for synthesizing these compounds plays a crucial role advancing development applications derivatives. Using density functional theory methods, we explored mechanism potential Rh(III)-catalyzed defluorinative annulation N-sulfonylarylamides with ethyl 2-diazo-3,3,3-trifluoropropanoates. Theoretical calculations indicate that initiates formation metal carbene via C–H activation denitrogenation, followed by migratory insertion. Subsequent steps involve metal-assisted β-fluoride elimination anion exchange. Finally, intramolecular cyclization, defluorination, sulfonyl migration yield products.

Language: Английский

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Assembly of Thiazino[3,4‐a]isoquinoline and Thiazepino[5,4‐a]isoquinoline Frameworks from Isoquinolinium 1,4‐Zwitterionic Thiolates via [5 + 1] and [5 + 2] Cycloaddition Reactions

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Abstract Two cycloaddition modes of isoquinolinium 1,4‐zwitterionic thiolates have been established. Upon choosing α ‐bromo ketones as the counterpart, a range isoquinoline‐fused thiazines can be attained with yields ranging from moderate to excellent through formal [5+1] reaction pathway, exhibiting remarkable substrate adaptability and resilience diverse functional groups. Additionally, library unprecedented thiazepino[5,4‐ ]isoquinolines, novel category seven‐membered heterocycles, has synthesized via [5+2] pathway utilizing acetylenedicarboxylate reactive component. Notably, this process stands out for its exceptional 100 % atomic utilization efficiency.

Language: Английский

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Six-membered ring systems: Pyridines and benzo analogs

Progress in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 309 - 354

Published: Jan. 1, 2024

Language: Английский

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