C–H activation-initiated spiroannulation reactions and their applications in the synthesis of spirocyclic compounds

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(12), P. 2324 - 2338

Published: Jan. 1, 2024

This review summarizes the most recent progress made in C–H bond activation-initiated spiroannulation reactions and their applications construction of structurally diverse biologically valuable spirocyclic scaffolds.

Language: Английский

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An unusual reaction mode of 1-phenylpyrazolidinones toward diazonaphthalen-2(1H)-ones featuring cascade C(sp²)–H and C(sp³)–H bond cleavage

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(13), P. 3238 - 3243

Published: Jan. 1, 2021

Herein, a novel synthesis of pyrazolidinone fused 1,3-benzooxazepine derivatives via formal [4 + 3] annulation reaction 1-phenylpyrazolidinones with diazonaphthalen-2(1H)-ones is presented.

Language: Английский

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Catalytic System‐Controlled Divergent Reaction Strategies for the Construction of Diversified Spiropyrazolone Skeletons from Pyrazolidinones and Diazopyrazolones

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(39), P. 21327 - 21333

Published: June 28, 2021

A catalytic system-controlled divergent reaction strategy was here reported to construct four types of intriguing spiroheterocyclic skeletons from simple and readily available starting materials via a precise chemical bond activation/[n+1] annulation cascade. The tetraazaspiroheterocyclic trizazspiroheterocyclic scaffolds could be independently constructed by selective N-N cascade, C(sp2 )-H activation/[4+1] novel tandem )-H/C(sp3 strategy, along with broad scope substrates, moderate excellent yields valuable transformations. More importantly, in these transformations, we are the first time capture activation C(sp3 pyrazolidinones under different system.

Language: Английский

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Synthesis of N-Arylindoles from 2-Alkenylanilines and Diazonaphthalen-2(1H)-ones through Simultaneous Indole Construction and Aryl Introduction

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(11), P. 7392 - 7404

Published: May 20, 2022

In this paper, an efficient synthesis of N-arylindoles through the cascade reaction 2-alkenylanilines with diazonaphthalen-2(1H)-ones is presented. Mechanistically, involves generation a Ru-carbene complex from diazonaphthalen-2(1H)-one, followed by carbene N-H bond insertion 2-alkenylaniline, intramolecular cyclization, and oxidative aromatization. reaction, Ru(II) acts as multifunctional catalyst to promote not only formation but also cyclization dehydrogenative Meanwhile, air green cost-effective oxidant. To our knowledge, first example in which were synthesized simultaneous introduction N-aryl unit construction indole scaffold. Notable advantages method include readily accessible halide-free substrates, additive-free conditions, good efficiency, excellent atom economy, compatibility diverse functional groups. addition, utility product thus obtained was showcased its structural transformations.

Language: Английский

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Copper‐Catalyzed C(sp³)− Functionalization and Annulation of 2‐Bromoaryl Oximes with Active Methylene Compounds towards Synthesis of Isoquinoline N‐Oxides

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(13), P. 2203 - 2210

Published: June 9, 2023

Abstract The established process proceeds through copper (II)‐catalyzed C( sp 3 )− functionalization of β ‐diketones/ ‐ketoesters with 2‐bromobenzaldehyde oximes followed by the intramolecular cyclization in situ generated acylated intermediates to deliver isoquinoline N ‐oxides. copper(II) acetate catalyzed C−H showed maximum efficacy at 60 °C methanol/toluene as solvent. described reaction conditions were applicable over a wide range substrates variety functional groups yield ‐oxides yields up 85%. developed approach was further elucidated means control experiments and DFT calculations.

Language: Английский

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Recent quinone diazide based transformations via metal–carbene formation

New Journal of Chemistry, Journal Year: 2021, Volume and Issue: 45(23), P. 10135 - 10149

Published: Jan. 1, 2021

Recent advancements in versatile synthetic transformations using quinone diazide based metal carbenes have been summarized.

Language: Английский

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Iridium(III)-Catalyzed Intermolecular Mild N-Arylation of Aliphatic Amides Using Quinoid Carbene: A Migratory Insertion-Based Approach

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(17), P. 10847 - 10854

Published: Aug. 17, 2021

An efficient Ir(III)-catalyzed straightforward intermolecular N-arylation of acyclic aliphatic amides has been achieved using quinone diazide as a coupling partner. The reaction developed under simple and mild conditions with broad substrate scope. bidentate picolinamide group is essential for successful transformation. Mechanistic studies DFT calculations highlighted the migratory insertion-based pathway. method exhibits different reactivities compared to reactions related diazo/azide congeners Rh(III)/Ir(III) catalysis.

Language: Английский

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Rh(III)-Catalyzed Spiroannulation Reaction of N-Aryl Nitrones with 2-Diazo-1,3-indandiones: Synthesis of Spirocyclic Indole-N-oxides and Their 1,3-Dipolar Cycloaddition with Maleimides

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3845 - 3858

Published: March 8, 2023

An efficient strategy for the preparation of spirocyclic indole-N-oxide compounds through a Rh(III)-catalyzed [4 + 1] spiroannulation reaction N-aryl nitrones with 2-diazo-1,3-indandiones as C1 synthons under extremely mild conditions is presented. From this reaction, 40 indole-N-oxides were easily obtained in up to 98% yield. In addition, title could be successfully used construction structurally intriguing maleimide-containing fused polycyclic scaffolds via diastereoselective 1,3-dipolar cycloaddition maleimides.

Language: Английский

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Enaminone-directed ruthenium(ii)-catalyzed C–H activation and annulation of arenes with diazonaphthoquinones for polycyclic benzocoumarins

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(88), P. 13187 - 13190

Published: Jan. 1, 2023

Weakly coordinating enaminone functionality has been leveraged for C–H activation strategy under ruthenium catalysis the regioselective annulative coupling of arenes with diazonaphthoquinones, offering polycyclic benzocoumarins in high yields.

Language: Английский

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Transition‐Metal‐Catalyzed Synthesis of Spiro Compounds through Activation and Cleavage of C−H Bonds

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(12)

Published: Nov. 22, 2022

Abstract Spirocyclic compounds represent an imperative class of naturally occurring substances characterized by their potential biological properties. They receive much attention as scaffolds in modern drug discovery programs and widespread applications asymmetric organic synthesis chiral catalysts ligands because structural rigidity excellent stereochemical recognition. With the advent C−H activation/annulation, enters into a new dimension with formation novel spiro cycles. The present review highlights advances transition‐metal‐catalyzed spirocyclic triggered bond activation.

Language: Английский

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