Application of sulfoxonium ylide in transition-metal-catalyzed C-H bond activation and functionalization reactions

Tetrahedron, Journal Year: 2021, Volume and Issue: 101, P. 132478 - 132478

Published: Oct. 8, 2021

Language: Английский

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Recent Advances in Transition-Metal-Catalyzed C–H Alkylation with Three-Membered Rings

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(4), P. 2330 - 2347

Published: Feb. 1, 2022

Transition-metal-catalyzed alkylation of (hetero)arenes with three-membered carbo-/heterocycles involving C–H activation and ring scission has been greatly developed over the past few years. The chelation-assisted strategies for controlling reactivity site selectivity in these protocols include use nitrogen-containing directing groups, pre-existing functional a Catellani-type intermediate, thereby providing rapid access to numerous oxygen- or heterocyclic systems. This review gives an update area various catalytic methodologies applications total synthesis natural products rings as alkylating reagents, which are classified into following three categories on basis employed strategies: (i) directed by (ii) (iii) aryl-NBE intermediates (Catellani-type cascade reaction).

Language: Английский

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Application of Sulfoxonium Ylides or Iodonium Ylides in Rhodium‐Catalyzed Synthesis of Phenanthrenes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1744 - 1750

Published: Feb. 22, 2024

Abstract The transmetalation triggered rhodium‐catalyzed C−H bond activation and tandem annulation of 2‐biphenylboronic acids with sulfoxonium ylides or iodonium has been developed. Various products phenanthrenes were constructed under redox‐neutral conditions in 34–86% yields. Several mechanism exploration experiments derivatization reactions conducted sequence to gain a deeper understanding the process potential this transformation. It offers an alternative approach for synthesis phenanthrene derivatives.

Language: Английский

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Rhodium(III)-Catalyzed [4 + 2] Annulation of N-Arylbenzamidines with Propargyl Alcohols: Highly Regioselective Synthesis of 1-Aminoisoquinolines Controlled by Noncovalent Interaction

Organic Letters, Journal Year: 2021, Volume and Issue: 23(17), P. 6628 - 6632

Published: Aug. 16, 2021

A highly regioselective synthesis of 1-aminoisoquinolines has been explored via rhodium(III)-catalyzed C–H bond activation/annulation reactions propargyl alcohols with N-arylbenzamidines. The imidamide was used as the directing group and nitrogen source heterocycle for regulating migratory insertion alcohol through a hydrogen bond. In this transformation, specific isomer obtained that would provide new strategy biological activity.

Language: Английский

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α-Carbonyl sulfoxonium ylides in transition metal-catalyzed C–H activation: a safe carbene precursor and a weak directing group

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(5), P. 879 - 909

Published: Dec. 6, 2022

Transition metal-catalyzed cross-coupling of sp2 C-H bonds with diazo compounds via carbene migratory insertion represents an efficient strategy for the construction C-C and C-heteroatom in organic synthesis. Despite popularity as coupling partners activation, they pose serious safety stability issues due to potential exothermic reactions linked release N2 gas. However, compared compounds, sulfoxonium ylides are generally crystalline solids, more stable, widely used industrial scales, easier/safer prepare. Therefore, recent years have witnessed upsurge employing α-carbonyl alternative surrogate transition activation. Unlike contain inherent serve a partner well weak directing group. This review will summarize progress made both categories reactions.

Language: Английский

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Comparison of Phosphonium and Sulfoxonium Ylides in Ru(II)-Catalyzed Dehydrogenative Annulations: A Density Functional Theory Study

Molecules, Journal Year: 2025, Volume and Issue: 30(9), P. 1883 - 1883

Published: April 23, 2025

Density functional theory calculations have been performed to explore the detailed mechanism of a ruthenium-catalyzed dehydrogenative annulation between α-carbonyl phosphonium ylide (A) and sulfoxonium (B). The proposed catalytic cycles consist several elementary steps in succession, namely C–H activation A, insertion B, reductive elimination, protodemetallation, an intramolecular Wittig reaction, which is rate-limiting, with free energy barrier 31.7 kcal/mol. As A B are both capable being substrate carbene precursor, there potentially four competing pathways including homo-coupling reactions. Further demonstrate that more reactive step than while opposite conclusion true for step, can successfully explain fact solely observed product originated from use as precursor. Molecular electrostatic potential, charge decomposition, electron density difference analyses were understand distinct behaviors two ylides nature key ruthenium–carbene intermediate.

Language: Английский

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Hydroxyl-Directed Ruthenium-Catalyzed peri-Selective C–H Acylmethylation and Annulation of Naphthols with Sulfoxonium Ylides

Organic Letters, Journal Year: 2021, Volume and Issue: 23(16), P. 6200 - 6205

Published: Aug. 2, 2021

Herein, we report a highly efficient ruthenium-catalyzed peri-selective C(sp2)–H acylmethylation of 1-naphthols with α-carbonyl sulfoxonium ylides by utilizing hydroxyl as weakly coordinating directing group. This new method imparts good reactivity, excellent chemo- and regioselectivity, broad functional group tolerance involves mild reaction conditions. The C–H acylmethylated products can be readily cyclized into fluorescent annulated pyrans one-pot process.

Language: Английский

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Rh(III) Catalyzed Redox-Neutral C–H Activation/[5 + 2] Annulation of Aroyl Hydrazides and Sulfoxonium Ylides: Synthesis of Benzodiazepinones

Organic Letters, Journal Year: 2023, Volume and Issue: 25(46), P. 8361 - 8366

Published: Nov. 14, 2023

We herein report the Rh(III) catalyzed redox-neutral C–H activation/[5 + 2] annulation of aroyl hydrazides with sulfoxonium ylides as safe carbene precursors. The reaction shows excellent functional group tolerance, broad substrate scope, and scalability. demonstrated synthetic utility protocol via synthesis various diazepam drug analogues, late-stage functionalization probenecid drug, large scale synthesis. Finally, kinetic studies revealed activation rate-determining step.

Language: Английский

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[Cp*IrCl₂]₂-Catalyzed Amidocarbonation of Olefins with Sulfoxonium Ylides toward Functionalized Isoindolin-1-ones

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7148 - 7153

Published: Sept. 26, 2023

A [Cp*IrCl2]2-catalyzed amidocarbonation of olefins with sulfoxonium ylides has been developed to generate diverse biologically important isoindolin-1-ones in high efficiency under mild reaction conditions. Mechanism studies indicated that this cascade was triggered by amino-iridation the olefin unit iridacycle, followed formal migratory insertion ylides. This newly method features broad substrate scopes and operational simplicity.

Language: Английский

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Rhodium(III)-Catalyzed Sequential Cyclization of N-Boc Hydrazones with Propargylic Monofluoroalkynes via C–H Activation/C–F Cleavage for the Synthesis of Spiro[cyclobutane-1,9′-indeno[1,2-a]indenes]

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(9), P. 6105 - 6114

Published: April 26, 2022

An effective rhodium(III) catalysis for the construction of valuable tetracyclic compounds is described herein. This domino process involving C–H activation/[3 + 2] annulation/intramolecular Friedel–Crafts reaction sequences simple and readily available N-Boc hydrazones propargylic monofluoroalkynes afforded fused spiro[cyclobutane-1,9′-indeno[1,2-a]indenes] in moderate to good yields, featuring three C–C bond formation. Moreover, control experiments indicated that activation might be involved rate-determining step.

Language: Английский

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