Rhodium(III)-Catalyzed Synthesis of Isoquinolines from Aryl Ketone <i>O</i>-Acyloxime Derivatives and Internal Alkynes

Too, Pei Chui; Wang, Yi‐Feng; Chiba, Shunsuke

doi:10.1021/ol102504b

Cited by 420 publications

(115 citation statements)

References 39 publications

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“…In polar solvents, O‐directed CH activation was favored to give intermediate III (path B), and the isomer 4 aa was produced through a similar process to that for 4 a . Under external‐oxidant‐free conditions, intermediate II might have undergone migratory insertion to give intermediate IV ,9, 12a, 14a which then afforded product 3 a after protonation in the nonpolar solvent (path C). However, in the presence of an Ag I species, sequential CH activation occurred (path D) to furnish intermediate V , which gave product 5 a after the second alkyne insertion and protonation processes.…”

Section: Resultsmentioning

confidence: 99%

Diversity‐Oriented Synthesis through Rh‐Catalyzed Selective Transformations of a Novel Multirole Directing Group

Wei

et al. 2015

ChemCatChem

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In the context of transition‐metal‐catalyzed CH functionalization, directing‐group strategy was developed for the improvement of chemical reactivity and selectivity. Recently, to avoid the inherent limitations of traditional mono‐role directing groups, a dual‐role oxidizing‐directing‐group strategy was developed, in which the directing group acts both as directing group and oxidant. Herein, we report a multirole directing group, which possesses multiple reactive sites, exhibits unique reactivity and selectivity, and leads to four different types of products from a single starting material through rhodium‐catalyzed CH activation/alkyne annulation reactions. The excellent product diversity and regio‐ and redox selectivity were well controlled by the tuning of solvents and oxidants.

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Section: Resultsmentioning

confidence: 99%

Diversity‐Oriented Synthesis through Rh‐Catalyzed Selective Transformations of a Novel Multirole Directing Group

Wei

et al. 2015

ChemCatChem

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“…We commenced our study by investigating the C−H amination of anisole ( 1 a ) with PivONH 3 OTf ( 2 a ; Piv=pivalate; Tf=trifluoromethanesulfonyl), which was first used by Fagnou et al. in the preparation of substrates containing an internal oxidant and by Morandi's group for aminohydroxylation of alkenes . Unfortunately, no obvious product was obtained from 1 a and 2 a (Table , entry 1).…”

Section: Methodsmentioning

confidence: 99%

Fe‐Catalyzed Amination of (Hetero)Arenes with a Redox‐Active Aminating Reagent under Mild Conditions

Liu

Shen

et al. 2016

Chemistry A European J

100

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A novel and efficient Fe-catalyzed direct C-H amination (NH ) of arenes is reported using a new redox-active aminating reagent. The reaction is simple, and can be performed under air, mild, and redox-neutral conditions. This protocol has a broad substrate scope and could be used in the late-stage modification of bioactive compounds. Mechanistic studies demonstrate that a radical pathway could be involved in this transformation.

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“…First, the oxidative addition of isoxazolone 1 a to a low-valent palladium center forms the six-membered palladacycle A, which readily undergoes decarboxylation [8,9] to give vinylnitrene/palladium complex B [10] and/or four-membered azapalladacyclobutene intermediate B'. First, the oxidative addition of isoxazolone 1 a to a low-valent palladium center forms the six-membered palladacycle A, which readily undergoes decarboxylation [8,9] to give vinylnitrene/palladium complex B [10] and/or four-membered azapalladacyclobutene intermediate B'.…”

Section: Entrymentioning

confidence: 99%

Palladium‐Catalyzed Decarboxylative Intramolecular Aziridination from 4H‐Isoxazol‐5‐ones Leading to 1‐Azabicyclo[3.1.0]hex‐2‐enes

et al. 2011

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Transition-metal-catalyzed nitrene-transfer reactions are powerful methods for incorporating nitrogen atoms directly into organic molecules. [1,2] Organic azides [2a,b] and N-sulfonyliminoiodinanes [2c-e] are highly reactive nitrene precursors, and have been widely used for such reactions as olefin aziridination and C À H amination. However, they must be handled carefully or prepared immediately before use because of their high reactivity. Therefore, the development of catalytic nitrene-transfer reactions that use stable precursors under mild reaction conditions is an important topic. Our research interest has been focused on 4H-isoxazol-5-ones, five-membered cyclic oxime esters, as candidates for stable vinylnitrene equivalents (Scheme 1). They can be readily prepared from bketoesters [3] and are generally thermally stable. We envisioned that the reaction of a 4H-isoxazol-5-one with a palladium catalyst would give a nitrene complex, [4] which is formed by the activation of the N À O bond by a low-valent palladium species [5] followed by decarboxylation. Herein, we report a palladium-catalyzed decarboxylative intramolecular aziridination reaction of alkene-tethered 4H-isoxazol-5-ones to form N-fused bicyclic aziridines.During the course of our investigations of several nitrenetransfer reactions using 4H-isoxazol-5-ones, we found that the reaction of 4H-isoxazol-5-one 1 a, which possesses a methallyl group at the 4-position, in the presence of 2.5 mol % of [Pd 2 (dba) 3 ] (5 mol % Pd) and 10 mol % of PPh 3 in 1,4-dioxane at 80 8C for 12 h gave the expected 1-azabicyclo[3

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Rhodium(III)-Catalyzed Synthesis of Isoquinolines from Aryl Ketone O-Acyloxime Derivatives and Internal Alkynes

Cited by 420 publications

References 39 publications

Diversity‐Oriented Synthesis through Rh‐Catalyzed Selective Transformations of a Novel Multirole Directing Group

Diversity‐Oriented Synthesis through Rh‐Catalyzed Selective Transformations of a Novel Multirole Directing Group

Fe‐Catalyzed Amination of (Hetero)Arenes with a Redox‐Active Aminating Reagent under Mild Conditions

Palladium‐Catalyzed Decarboxylative Intramolecular Aziridination from 4H‐Isoxazol‐5‐ones Leading to 1‐Azabicyclo[3.1.0]hex‐2‐enes

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