Reverse Regioselective Cp*Co(III)-Catalyzed [4 + 2] C–H Annulation of N-Chloroamides with Vinylsilanes: Synthesis of 4-Silylated Isoquinolones and Their Synthetic Utilities

Organic Letters, Journal Year: 2023, Volume and Issue: 25(43), P. 7878 - 7883

Published: Oct. 23, 2023

We have developed a Cp*Co(III)-catalyzed reverse regioselective [4 + 2] annulation of N-chlorobenzamides/acrylamides with vinylsilanes for the synthesis 4-silylated isoquinolones. The reaction was performed at ambient temperature under redox-neutral conditions. utilized N-Cl bond as an internal oxidant, furnished required products excellent regioselectivities, and demonstrated high functional group tolerance. synthetic utility isoquinolones has been preparation 4-heteroarylated 4-alkylated via metal-free C-C couplings. Additionally, 3,4-dihydroisoquinolones were synthesized protodesilylation isoquinolones, thus making vinylsilane ethylene surrogate.

Language: Английский

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Construction of 3,4-Dihydroquinolone Derivatives through Pd-Catalyzed [4+2] Cycloaddition of Vinyl Benzoxazinanones with α-Alkylidene Succinimides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3279 - 3291

Published: Feb. 20, 2024

The construction of 3,4-dihydroquinolone derivatives has attracted a considerable amount attention due to their extensive applications in medicinal chemistry. In this study, we present the Pd-catalyzed [4+2] cycloaddition vinyl benzoxazinanones with α-alkylidene succinimides for efficient synthesis 3,4-dihydroquinolones. This approach presents numerous advantages, including ready availability starting materials, mild reaction conditions without use additional bases, and wide range substrates. particular, all desired products can be easily afforded high yields (≤99%) excellent diastereoselectivities (>20:1). practicality reliability strategy were demonstrated by successful scale-up subsequent straightforward synthetic transformations.

Language: Английский

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Co(III)-Catalyzed Regioselective Benzannulation of Substituted Pyridones with 1,6-Diynes via Dual C-H Bond Activation

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(63), P. 8296 - 8299

Published: Jan. 1, 2024

A Co(III)-catalyzed site-selective C5 and C6 benzannulation of substituted pyridones with 1,6-diynes

Language: Английский

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Cp*Co(III)-catalyzed ortho-alkylation/alkenylation of anilides

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A highly practical and efficient Cp*Co( iii )-catalyzed regioselective C–H alkylation/alkenylation of anilides with maleimides acrylates was developed, during which a weakly coordinating amide group functioned as the directing group.

Language: Английский

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Condition‐Controlled Selective Synthesis of CF₃‐Chromene and CF₃‐Benzofuran from N‐Phenoxyacetamide and CF₃‐Ynone

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

Published: March 27, 2025

Comprehensive Summary Presented herein is a condition‐controlled selective synthesis of CF 3 ‐chromene and ‐benzofuran based on the reaction N ‐phenoxyacetamide ‐ynone. When carried out in MeOH under catalysis Rh(III), formed via C—H metalation‐initiated alkenylation, acetamide group migration intramolecular oxo ‐nucleophilic addition. On other hand, when run DMSO promotion CsOAc, generated aza ‐Michael addition‐initiated [3,3]‐σ rearrangement, addition water elimination. To our knowledge, this first report construction chromene or benzofuran scaffold along with introduction unit from same starting materials. The methodology was scalable products could be readily transformed into valuable products. Moreover, thus obtained possess decent anticancer activity.

Language: Английский

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Harnessing Vinyl Acetate as an Acetylene Equivalent in Redox-Neutral Cp*Co(III)-Catalyzed C–H Activation/Annulation for the Synthesis of Isoquinolones and Pyridones

ACS Omega, Journal Year: 2023, Volume and Issue: 8(28), P. 25262 - 25271

Published: July 5, 2023

We have developed Cp*Co(III)-catalyzed redox-neutral synthesis of 3,4-unsubstituted isoquinoline 1(2H)-ones at ambient temperature using N-chloroamides as a starting material. The reaction utilizes vinyl acetate an inexpensive and benign acetylene surrogate. N-Cl bond the N-chlorobenzamides plays role internal oxidant hence precludes need for external oxidant. works with wide range substrates having various functional groups substrate containing heterocyclic ring. Notably, is extended to N-chloroacrylamides in which vinylic C-H activation occurs furnish 2-pyridone derivatives. Preliminary mechanistic studies were also conducted shed light on mechanism this reaction.

Language: Английский

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Photoredox/Iron Dual-Catalysis-Enabled [4 + 2] Cyclization of Acyl Nitrene with Alkynes

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

In this work, the annulation of acyl nitrene with alkynes is reported under photoredox/iron dual-catalysis for synthesis a series isoquninalin-2-ones. The reaction featured high regioselectivity and good generality. particular, resulting isoquinalin-2-ones could be structurally elaborated into several biologically interesting scaffolds. Mechanism investigation suggests that was ascribed to formal [4 + 2] cyclization. It believed represents an initial example preparing isoquinolin-1-ones from ferric peroxyl-catalyzed insertion.

Language: Английский

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Ru(II)-Catalyzed C(sp²)–H Activation Annulation: Synthesis of Fluorescent Benzoisoquinolonyl Acetate/Peptides from N-Arylamides and Ethyne at Room Temperature

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7485 - 7494

Published: May 15, 2024

Benzoisoquinolones are aryl ring extended isoquinolinone derivatives, which constituents of alkaloid natural products. This report describes the synthesis novel benzoisoquinolone amino acid/peptide derivatives from respective

Language: Английский

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Redox-neutral access to isoquinolines via cobalt(III)-catalyzed C H acylmethylation/cyclization of benzimidates with sulfoxonium ylides

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 146, P. 155185 - 155185

Published: July 7, 2024

Language: Английский

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M^IV/Co^–I (M = Zr, Hf) Bis(phosphinoamide) Complexes with η⁶- and η⁴-Arenes

Organometallics, Journal Year: 2024, Volume and Issue: 43(17), P. 1837 - 1851

Published: Aug. 14, 2024

Despite their relevance to catalysis, low-/subvalent cobalt complexes are difficult synthesize and isolate. Consequently, very few "cobaltate" known there is a lack of architectural diversity in this field. Lewis acidic d0 group IV metals have been demonstrated stabilize Co–I centers via metal–metal bonds. Herein, we report the synthesis bis(phosphinoamide) heterobimetallic MIV/Co–I arene (M = Zr, Hf). The driving force maintain aromaticity arenes dictates hapticity Co-bound ligands influences binding arrangement phosphinoamide ligands. Benzene toluene were observed bind η6 center, forcing dissociation one ligands, whereas η4-coordination anthracene allows both remain bound Co center. identity metal ion starkly influence lability arene. For instance, benzene ligand ZrIV/Co–I complex rapidly exchanges with C6D6 solution, toluene/C6D6 exchange much slower appreciable C6H6/C6D6 not for Hf analogue. loses upon repeated exposure vacuum form an arene-free tetrametallic dimer.

Language: Английский

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