Palladium-Catalyzed Synthesis of 3-Haloindol-2-amines from 3-Diazoindolin-2-imines and Alkyl Halides

Zhou, Yuxuan; Li, Zhenmin; Ma, Fanghui; Zhao, Chang; Lü, Ping; Wang, Yanguang

doi:10.1021/acs.joc.9b00191

Cited by 9 publications

(4 citation statements)

References 50 publications

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“…Recently, Wang and Lu developed a Pd-catalyzed synthesis of 3-haloindol-2-amines 253.3 from 3-diazoindolin-2-imines 253.1 and alkyl halides 253.2 under mild reaction conditions (Scheme ). Pd 2 (dba) 3 and K 2 CO 3 were found to be the most effective reagent combination during screening of the reaction conditions. Various 3-diazoindolin-2-imines efficiently reacted with a range of alkyl, allyl, and benzyl bromides, allyl chlorides, alkyl iodides, α-bromo ketones, and carboxylic esters to furnish diverse 3-haloindol-2-amines in good to excellent yields.…”

Section: Denitrogenative Transformations Of Triazoloindolesmentioning

confidence: 99%

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

2022

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Readily accessible and shelf-stable 1,2,3-triazole and its analogues such as pyridotriazole, triazoloindole, benzotriazole, and thiadiazole exist in equilibrium with their ring-opened isomers, viz., diazo compounds. These ring-opened isomers could be trapped by various metal catalysts (e.g., Rh, Pd, Cu, Co, Ag, etc.) to generate the corresponding metal carbenoids with extrusion of nitrogen. As a consequence, these unique N-heterocycles facilitate access to a realm of N-containing complex structural motifs of biological importance through denitrogenative transformations such as transannulations, insertions, ylide formation, and rearrangements by trapping of the metal carbenoids with a diverse range of coupling partners (e.g., alkenes, alkynes, nitriles, carbo/heterocycles, X–H/C–X bonds, etc.). Hence, suitably substituted triazole derivatives have emerged as efficient surrogates of diazo compounds for the generation of reactive metal carbenoids during the past decades. In this comprehensive review, we aim to discuss in detail the remarkable advancement in their synthesis and synthetic applications.

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Section: Denitrogenative Transformations Of Triazoloindolesmentioning

confidence: 99%

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

2022

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“…A palladium catalyzed insertion of 237 into the CÀ X bond of alkyl halides 268 was achieved by Wang's group to prepare synthetically useful 3-haloindol-2-amines 269 (Scheme 64). [81] A wide range of 237 along with different alkyl and allylic halides and α-bromo ketones/carboxylic esters were employed and the corresponding 3-haloindol-2-amines 269 were isolated in good to excellent yields. As a synthetic application of this protocol, N-allyl-3-iodoindol-2-amines were smoothly converted to biologically important pyrrolo [2,3-b]indoles 270 by using palladium(II)-catalyzed intramolecular Heck reaction.…”

Section: Insertion Reaction Of 3-diazoindolin-2-iminesmentioning

confidence: 99%

Catalytic Insertion Reactions of α‐Imino Carbenoids

Pal

Volla

2021

The Chemical Record

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Over the past decade, α-imino carbenoids generated via transition metal (such as rhodium, nickel, copper, palladium, silver) catalyzed denitrogenative ring-opening of N-sulfonyl-1,2,3-triazoles have found an extensive account of applications in synthetic organic chemistry. Particularly, they have been widely utilized as a donor/acceptor carbene complex in a range of transformations leading to diverse nitrogen containing compounds and heterocycles. Along the same direction, 3-diazoindolin-2-imines were successfully applied as an alternative source of αimino carbenoid precursors for the development of a number of methodologies to access diverse indole derivatives. This review summarizes the insertion reactions of α-imino metal carbenes derived from N-sulfonyl-1,2,3-triazoles and 3-diazoindolin-2-imines.

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“…By utilizing the copper(I)-catalyzed reaction of 2-ethynylanilines with sulfonyl azides or the Huisgen-type cycloaddition of indoles with sulfonyl azides, we developed practical methods for the preparation of 3-diazoindolin-2-imines in a single step in 2014 (Figure ). This class of cyclic α-diazo imidamides has been widely investigated by us and other groups, and a variety of indole-containing heterocycles were thus conveniently synthesized. , Encouraged by this success, we further prepared 4-diazoisochroman-3-imines by the copper(I)-catalyzed reaction of (2-ethynylphenyl) methanols with sulfonyl azides in 2017 . 4-Diazoisochroman-3-imines contain a cyclic α-diazo imidate substructure and could be used as metal carbene precursors for cyclopropanation, transannulation, and C–H functionalization of N -methoxybenzamides and N -alkylbenzamidines .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 8-Alkoxy-5H-isochromeno[3,4-c]isoquinolines and 1-Alkoxy-4-arylisoquinolin-3-ols through Rh(III)-Catalyzed C–H Functionalization of Benzimidates with 4-Diazoisochroman-3-imines and 4-Diazoisoquinolin-3-ones

Xie

Lü

et al. 2020

J. Org. Chem.

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Rh(III)-catalyzed C–H activation/annulation of benzimidates with 4-diazoisochroman-3-imines furnished 8-alkoxy-5H-isochromeno[3,4-c]isoquinolines in moderate to excellent yields with a broad range of substrate scope. The reaction was carried out under mild reaction conditions and could be scaled up with practical usage. Similar reaction between benzimidates and 4-diazoisoquinolin-3-ones provided 1-alkoxy-4-arylisoquinolin-3-ols in excellent yields. Moreover, the synthesized products could be conveniently transformed to the corresponding heterocycles with a 1,8-naphthyridinone or isochromenopyridinone core, which are privileged structures in medicinal chemistry.

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Palladium-Catalyzed Synthesis of 3-Haloindol-2-amines from 3-Diazoindolin-2-imines and Alkyl Halides

Cited by 9 publications

References 50 publications

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

Catalytic Insertion Reactions of α‐Imino Carbenoids

Synthesis of 8-Alkoxy-5H-isochromeno[3,4-c]isoquinolines and 1-Alkoxy-4-arylisoquinolin-3-ols through Rh(III)-Catalyzed C–H Functionalization of Benzimidates with 4-Diazoisochroman-3-imines and 4-Diazoisoquinolin-3-ones

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