Rh(III)-Catalyzed C–H Activation/Cycloisomerization of <i>N</i>-Phenoxyacetamides with Enynones for One-Pot Assembly of Furylated 2-Alkenylphenols

Chen, Weijie; Liu, Fu‐Xiaomin; Bian, Mengyao; Li, Liping; Zhou, Zhi; Yi, Wei

doi:10.1021/acs.joc.9b02534

Cited by 10 publications

(4 citation statements)

References 88 publications

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“…The similar Cp*Rh(III)‐catalyzed domino process of C−H bond activation, carbene formation, and migratory insertion has also been applied to the synthesis of alkenylphenol‐substituted furans 53 using N ‐phenoxyacetamides 52 and enynones 1 (Scheme 21). [30] This domino process was developed by the Yi group, wherein oxidizing‐directing‐group (−O−NHAc)‐assisted aryl C(sp 2 )−H bond activation of N ‐phenoxyacetamides 52 was catalyzed by Cp* Cy Rh(III), enabling a redox‐neutral process. The reaction is initiated by anion exchange of the rhodium catalyst to generate active Cp* Cy Rh(III) catalyst I , followed by −ONHAc‐directed redox‐neutral C(sp 2 )−H activation, forming five‐membered rhodacycle II .…”

Section: Furyl Metal Carbene X−h Insertion Reactions Using Enynones O...mentioning

confidence: 99%

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Cho,

Kim

2024

Asian J Org Chem

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Enynones and enynals represent donor‐type carbene precursors that efficiently form furyl metal carbenes via a catalytic intramolecular 5‐exo‐dig cyclization and rearrangement cascade, in a 100% atom‐economical manner, using various metals. These furyl metal carbenes have been successfully utilized in numerous carbene reactions, including metal carbene X–H insertion, cyclopropanations, metathesis, and cross‐coupling, demonstrating a broad reaction scope and efficiency in constructing highly functionalized furans. Recent years have witnessed significant advancements in transformations involving furyl metal carbenes, especially in asymmetric carbene insertion reactions, domino reactions involving zwitterionic intermediates, various rearrangement strategies, and their application in synthesizing functional materials and drug candidates. In this review, we summarize recent progress in furyl metal carbene reactions generated from enynones and enynals, focusing on the synthesis of highly functionalized furans.

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Section: Furyl Metal Carbene X−h Insertion Reactions Using Enynones O...mentioning

confidence: 99%

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Cho,

Kim

2024

Asian J Org Chem

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“…Over the past decade, transition-metal-catalyzed chelation-assisted direct C–H functionalization of (hetero)arenes through tandem C–H activation/carbene migratory insertion has been proven to be a highly efficient and versatile strategy, which is widely applied in various transformations such as C–H alkylations, arylations, alkenylations, as well as annulations . Despite the recent remarkable advances in this area, most of the reported reactions employed diazo substrates as effective carbene precursors, which are unstable and potentially explosive in nature. , To overcome these problems, several relatively safe and easily available nondiazo carbene surrogates such as triazoles, enynones, N -tosylhydrazones, iodonium ylides, and sulfoxonium ylides have been successfully utilized as coupling reagents in plenty of C–H functionalization reactions. Among them, iodonium ylides can be readily prepared from the corresponding active methylene compounds with iodobenzene diacetate and have been employed as a versatile synthon in synthetic organic chemistry due to their easy accessibility, good thermal stability, and rich reactivity .…”

Section: Introductionmentioning

confidence: 99%

Three-Component Synthesis of Isoquinolone Derivatives via Rh(III)-Catalyzed C–H Activation and Tandem Annulation

Yang

Liu

et al. 2022

J. Org. Chem.

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A one-pot three-component synthesis of multifunctionalized isoquinolones from 2-oxazolines, iodonium ylides, and carboxylic acids via Rh(III)-catalyzed oxazolinyl-directed C−H activation and tandem annulation under redox-neutral conditions has been developed. This catalytic system is characterized by readily available starting materials, a wide tolerance of functional groups, a short reaction time, and high yields. The synthetic utility of the cascade reaction was further demonstrated by a gram-scale synthesis and derivatization of the obtained products.

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“…Considering the potential divergent reactivities of methylenecyclopropanes and in combination with the highly reactive Rh(V) intermediates derived from N -phenoxy amides, we envisaged that the fine-tuning of different reaction parameters might stabilize particular rhodacycle intermediates, and thus switch the reaction pathway to afford chemodivergent products 52 – 55 . Herein, we report diverse synthesis of ortho -functionalized phenols and their derivatives via Rh(III)-catalyzed C–H couplings of N -phenoxyacetamides with methylenecyclopropanes in a tunable manner.…”

Section: Introductionmentioning

confidence: 99%

Chemodivergent assembly of ortho-functionalized phenols with tunable selectivity via rhodium(III)-catalyzed and solvent-controlled C-H activation

et al. 2021

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Ortho-functionalized phenols and their derivatives represent prominent structural motifs and building blocks in medicinal and synthetic chemistry. While numerous synthetic approaches exist, the development of atom-/step-economic and practical methods for the chemodivergent assembly of diverse ortho-functionalized phenols based on fixed catalyst/substrates remains challenging. Here, by selectively controlling the reactivities of different sites in methylenecyclopropane core, Rh(III)-catalyzed redox-neutral and tunable C-H functionalizations of N-phenoxyacetamides are realized, providing access to both ortho-functionalized phenols bearing linear dienyl, cyclopropyl or allyl ether groups, and cyclic 3-ethylidene 2,3-dihydrobenzofuran frameworks under mild cross-coupling conditions. These divergent transformations feature broad substrate compatibility, synthetic applications and excellent site-/regio-/chemoselectivity. Experimental and computational mechanistic studies reveal that distinct catalytic modes involving selective β-C/β-H elimination, π-allylation, inter-/intramolecular nucleophilic substitution cascade and β-H’ elimination processes enabled by different solvent-mediated and coupling partner-controlled reaction conditions are crucial for achieving chemodivergence, among which a structurally distinct Rh(V) species derived from a five-membered rhodacycle is proposed as the corresponding active intermediates.

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Rh(III)-Catalyzed C–H Activation/Cycloisomerization of N-Phenoxyacetamides with Enynones for One-Pot Assembly of Furylated 2-Alkenylphenols

Cited by 10 publications

References 88 publications

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Three-Component Synthesis of Isoquinolone Derivatives via Rh(III)-Catalyzed C–H Activation and Tandem Annulation

Chemodivergent assembly of ortho-functionalized phenols with tunable selectivity via rhodium(III)-catalyzed and solvent-controlled C-H activation

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