Redox-neutral C–H annulation strategies for the synthesis of heterocycles via high-valent Cp*Co(iii) catalysis

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(19), P. 3918 - 3941

Published: Jan. 1, 2023

This review demonstrates the redox-neutral synthetic approaches towards valuable heterocycles such as isoquinolines, indoles, isoquinolones, and tetrahydroquinolines via high-valent Cp*Co( iii ) catalysis.

Language: Английский

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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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Co(III)-Catalyzed Three-Component Assembling of 2-Pyridones with Dienes and Formaldehyde via C–H Bond Activation

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

Published: March 24, 2025

Here, we have demonstrated a Co(III)-catalyzed C–H functionalization of substituted pyridones with dienes and para-formaldehyde via three-component sequential reaction. A library homoallylic alcohols is synthesized high regio- chemoselectivity. The reaction scope widely compatible various N-pyridyl-2-pyridones, butadiene, dienes. Interestingly, N-pyridyl-4-pyridone also participated in the product was further converted into dihydrofuran-derived N-pyridyl-2-pyridone derivatives. convincing mechanism mechanistic investigations are described to justify current methodology.

Language: Английский

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Ru(II)-Catalyzed Regioselective Redox-Neutral [4 + 2] Annulation of N-Chlorobenzamides with 1,3-Diynes at Room Temperature for the Synthesis of Isoquinolones

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(7), P. 4704 - 4719

Published: March 9, 2023

Herein, we report Ru(II)-catalyzed C-H/N-H bond functionalization of N-chlorobenzamides with 1,3-diynes via regioselective (4 + 2) annulation for the synthesis isoquinolones under redox-neutral conditions at room temperature. This represents first example C-H using an inexpensive and commercially available [Ru(p-cymene)Cl2]2 catalyst. The reaction is operationally simple, works in absence any silver additives, also applicable to a broad range substrates good functional group tolerance. synthetic utility isoquinolone demonstrated bis-heterocycles consisting isoquinolone-pyrrole isoquinolone-isocoumarin scaffolds.

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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Recent Advances in the 3 d‐Transition‐Metal‐Catalyzed Synthesis of Isoquinolines and its Derivatives

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4458 - 4494

Published: Nov. 24, 2023

Abstract The preservation of scarce rare earth metals, such as palladium, rhodium, iridium, and others, poses a significant challenge for humanity due to their limited availability. These metals might be replaced by earth‐abundant 3d‐transition cobalt, manganese, iron, nickel, copper, etc . Isoquinolines have acquired an important position in synthetic organic chemistry well medicinal chemistry. They manifest diverse range natural molecules, serving pivotal synthons the synthesis numerous bioactive compounds with notable significance. Numerous reports on isoquinoline derivatives via transition metal catalysis been published worldwide. In this review, we summarize recent approaches synthesizing various using 3d‐transition‐metal catalysts since 2020. review has divided into different 3d‐transition‐metal‐based catalysis. We expect that will bring better overview present status progress made isoquinolines persuade more advancements research area near future.

Language: Английский

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Cobalt(III)-Catalyzed Regioselective [4 + 2]-Annulation of N-Chlorobenzamides with Substituted Alkenes

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(19), P. 13073 - 13088

Published: Sept. 26, 2022

A Co(III)-catalyzed redox-neutral [4 + 2] annulation of N-chlorobenzamides/acrylamides with substituted alkenes at ambient temperature is demonstrated. Using this protocol, pharmaceutically important 3,4-dihydroisoquinolinone derivatives were synthesized in good yields. Intriguingly, the synthetically useful functional group allylic coupling partners such as sulfonyl, carbonate, acetate, phosphate, amide, nitrile, and silane retained final cyclized product. The present reaction was compatible various benzamides partners. To support proposed mechanism, competition experiments, deuterium labeling studies, kinetic isotope effect studies performed.

Language: Английский

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Palladium-Catalyzed C–H Allylation/Annulation Reaction of Amides and Allylic Alcohols: Regioselective Construction of Vinyl-Substituted 3,4-Dihydroisoquinolones

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3871 - 3882

Published: March 2, 2023

A palladium-catalyzed highly regioselective C–H allylation/annulation reaction of N-sulfonyl amides with secondary or tertiary allylic alcohols has been developed to construct 3,4-dihydroisoquinolones bearing a synthetically valuable vinyl substituent. This cascade cyclization approach involving allylation not reported previously. The commercially available alcohol substrates, the only by-product water, and used terminal oxidant O2 provide environmentally benign advantages.

Language: Английский

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Co(III) ‐Catalyzed Regioselective [4+2]‐Annulation of N‐Chlorobenzamide with Allenes and Vinyl Acetate

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 13(1)

Published: Nov. 28, 2023

Abstract A regioselective annulation protocol of N ‐chlorobenzamide with allenes and vinyl acetate is reported using a less expensive catalytic system, i. e . Co(III) catalysis Na 2 CO 3 as base. (CO) NH−Cl acts both, an internal oxidant directing group. Allenes are successfully annulated ‐chlorobenzamide, providing different exocyclic isoquinolone derivatives in good to moderate yield. Notably, acetylene surrogate undergoes the developed provide excellent Interestingly, situ deprotection acetyl group allowed quantitative synthesis hydroxyisoquinolone.

Language: Английский

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Nucleophilic aromatization of monoterpenes from isoprene under nickel/iodine cascade catalysis

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 4, 2023

As a large number of organic compounds possessing two isoprene units, monoterpenes and monoterpenoids play important roles in pharmaceutical, cosmetic, agricultural, food industries. In nature, are constructed from geranyl pyrophosphate (C10) via various transformations. Herein, the bulk C5 chemical-isoprene, is used for creation nucleophilic aromatization under cascade catalysis nickel iodine. Drugs oil mixtures conifer lemon can be convergently transformed to desired monoterpenoid. Preliminary mechanistic studies conducted get insights about reaction pathway. Two types cyclic respectively introduced onto similar heterocycles orthogonal C-H functionalization. And hybrid terpenyl indoles programmatically assembled abundant or C10 blocks. This work not only contributes high chemo-, regio-, redox-selective transformation isoprene, but also provides complementary approach unnatural monoterpenoids.

Language: Английский

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