Catalyst-Controlled Switchable (5 + 4)/(3 + 4) Cycloadditions for the Divergent Synthesis of Pyrazole-Fused Seven- and Nine-Membered Heterocycles

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(16), P. 10694 - 10704

Published: Aug. 1, 2023

Developing diversity-oriented synthetic approaches for medium-sized rings is of great interest, and the divergent synthesis with different ring sizes poses a challenging task. In this study, we present catalyst-controlled switchable (5 + 4)/(3 4) cycloaddition strategy seven- nine-membered heterocycles. Utilizing two 4-aminopyridine Lewis base catalysts, pyrazole-fused benzazepines or benzoxazonines can be efficiently assembled from same substrates. These products exhibit good stability without interconversion under reaction conditions elevated temperatures. The origin chemoselectivity was elucidated by means computational studies involving DFT calculations, distortion/interaction analysis, noncovalent interaction analysis.

Language: Английский

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Chemodivergent Parallel Kinetic Resolution of Paracyclophanes: Enantiomer Fishing with Different Substrates

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: July 25, 2024

Abstract An unprecedented chemodivergent strategy for parallel kinetic resolution (PKR) is disclosed through which two planar chiral products bearing different structures were simultaneously afforded with opposite stereoselectivities. Two achiral esters are activated by one single N‐heterocyclic carbene (NHC) catalyst to react the enantiomers of racemic imine substrate in a fashion. distinct and stereoselectivities respectively from same reaction system good excellent yields, enantio‐ diastereoselectivities. Control experiments studies carried out probe dynamic properties during progress. The pyridine lactam show interesting applications both asymmetric synthesis pesticide development.

Language: Английский

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Silver/chiral pyrrolidinopyridine relay catalytic cycloisomerization/(2 + 3) cycloadditions of enynamides to asymmetrically synthesize bispirocyclopentenes as PDE1B inhibitors

Communications Chemistry, Journal Year: 2023, Volume and Issue: 6(1)

Published: June 19, 2023

Significant progress has been made in asymmetric synthesis through the use of transition metal catalysts combined with Lewis bases. However, a dual catalytic system involving 4-aminopyridine and received little attention. Here we show metal/Lewis base relay featuring silver acetate modified chiral pyrrolidinopyridine (PPY). It was successfully applied cycloisomerization/(2 + 3) cycloaddition reaction enynamides. Bispirocyclopentene pyrazolone products could be efficiently synthesized stereoselective economical manner (up to >19:1 dr, 99.5:0.5 er). Transformations product access stereodivergent diastereoisomers densely functionalized polycyclic derivatives. Mechanistic studies illustrated model origin uncommon chemoselectivity. In subsequent bioassays, containing privileged drug-like scaffold exhibited isoform-selective phosphodiesterase 1 (PDE1) inhibitory activity vitro. The optimal lead compound displayed good therapeutic effect for ameliorating pulmonary fibrosis via inhibiting PDE1 vivo.

Language: Английский

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1,3-Indanedione: An versatile building block

Green Synthesis and Catalysis, Journal Year: 2022, Volume and Issue: 4(2), P. 78 - 88

Published: Dec. 14, 2022

Indanone-containing compounds are very important components of various natural products, chemical drugs, agrochemicals and functionalized material fields. 1,3-Indanedione is a typical cyclic 1,3-dicarbonyl compound with three contiguous reactive electrophilic nucleophilic sites. The easily prepared 2-arylidene-1,3-indanediones active α,β-unsaturated carbonyl could act as 1,3-dipolarophile, 1,4-dienophile 1-oxa-1,3-diene, etc. On the other hand, homodimer (bindone) cyclotrimer (truxenone) derived from base-catalyzed self-condensation 1,3-indanedione also compounds. Therefore, its derivatives can be employed key substrates in domino multicomponent reactions. In this review, we summarized recent progress on reactions 1,3-indanedione, especially our achievements synthetic applications for complex indanone-containing carbocyclic heterocyclic

Language: Английский

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DMAP Catalyzed Ring-Opening/Cycloaddition of Vinyl Oxiranes with Activated Ketone Compounds to Construct the 1,3-Dioxolane Skeletons

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9322 - 9327

Published: Oct. 24, 2024

The present work develops a DMAP-catalyzed [3 + 2] cycloaddition of vinyl oxiranes with activated ketone compounds, affording dioxolane derivatives moderate to excellent yields. This approach represents the first Lewis base (LB)-catalyzed ring-opening reaction epoxides, simultaneously providing rare oxygen-containing active intermediate in this field. gram-scale preparation and facile derivatization cycloadduct highlight significant synthetic potential strategy.

Language: Английский

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Organocatalytic (5+1) benzannulation of Morita–Baylis–Hillman carbonates: synthesis of multisubstituted 4-benzylidene pyrazolones

New Journal of Chemistry, Journal Year: 2022, Volume and Issue: 46(24), P. 11617 - 11622

Published: Jan. 1, 2022

DABCO-catalyzed (5+1) cycloaddition of MBH carbonate undergoes an α-double deprotonation pathway to de novo assemble the benzene ring.

Language: Английский

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DMAP-Catalyzed [4+3] Spiroannulation of Pyrazolone-Derived Morita–Baylis–Hillman Carbonates with N-(o-Chloromethyl)aryl Amides to Forge Spiro[pyrazolone-azepine] Scaffolds

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(14), P. 10190 - 10198

Published: June 30, 2023

A novel DMAP-catalyzed [4+3] spiroannulation of pyrazolone-derived Morita-Baylis-Hillman carbonates with N-(o-chloromethyl)aryl amides was developed. This reaction led to the assembly medicinally relevant pyrazolone and azepine nuclei into a structurally new spirocyclic scaffold, diverse array spiro[pyrazolone-azepine] products were afforded in good excellent yields (up 93%) wide substrate scope (23 examples) under mild conditions. Moreover, gram-scale product transformations conducted, which further increased diversity products.

Language: Английский

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Synthesis of functionalized spiro[indanone-benzazepine] scaffolds via [4 + 3] annulation reaction of N-(o-chloromethyl)aryl amides with ninhydrin-derived Morita−Baylis−Hillman carbonates

Tetrahedron, Journal Year: 2023, Volume and Issue: 150, P. 133772 - 133772

Published: Dec. 1, 2023

Language: Английский

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Phosphine‐Catalyzed Domino Annulation Reactions of o‐Aminotrifluoroacetophenone Derivatives with Morita–Baylis–Hillman Carbonates: Construction of Tetrahydrofuro[3,2‐b]indolines

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(10), P. 2252 - 2256

Published: April 5, 2024

Abstract The domino annulation reactions of o ‐aminotrifluoroacetophenone derivatives and MBH carbonates enabled by PPh 3 have been reported, which provide a series tetrahydrofuro[3,2‐b]indolines containing CF ‐substituted tetrasubstituted carbon stereocenters in yields 74 to 95% >20:1 dr. In this process, were used as C1/C3 synthons. MTT assay shows that the products exhibit activity inhibitory effect on proliferation Hela cancer cell line.

Language: Английский

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Asymmetric [3+2] spiroannulation of pyrazolone-derived Morita–Baylis–Hillman carbonates with alkynyl ketones: facile access to spiro[cyclopentadiene-pyrazolone] scaffolds

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(68), P. 9504 - 9507

Published: Jan. 1, 2022

An organocatalyzed asymmetric [3+2] spiroannulation reaction of pyrazolone-derived MBH carbonates with alkynyl ketones was described, affording chiral spiro[cyclopentadiene-pyrazolone] scaffolds in good yields high degrees enantiocontrol.

Language: Английский

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