Photoredox catalyzed cascade CF<sub>3</sub> addition/chemodivergent annulations of <i>ortho</i>-alkenyl aryl ureas

Babu, Sakamuri Sarath; Varma, Anand; Gopinath, Purushothaman

doi:10.1039/d1cc06289a

Cited by 8 publications

(3 citation statements)

References 26 publications

(4 reference statements)

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“…A photocatalytic approach was disclosed by Gopinath and co-workers for the preparation of 2-amino-1,3-benzoxazepines and dihydroquinazolinones (Scheme 44) [52]. By controlling the substituents on 2-alkenyl aryl urea substrates, the researchers could achieve two different heterocycles under the ruthenium photoredox catalyst.…”

Section: S C H E M E 3mentioning

confidence: 99%

2‐Vinylaniline in the synthesis of heterocycles: Recent advances

Doraghi,

Navid,

Karimian

et al. 2024

Journal of Heterocyclic Chem

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Abstract2‐Vinylanilines are readily accessible substrates, which are undoubtedly one of the best candidates for the construction of diversely nitrogen‐containing heterocyclic compounds. Owing to the amine and alkenyl groups in their structures, these frameworks offer a facile, direct, and selective synthetic method. This review describes various cyclization reactions involving 2‐vinylanilines catalyzed by transition metals, or under metal‐free conditions.

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Section: S C H E M E 3mentioning

confidence: 99%

2‐Vinylaniline in the synthesis of heterocycles: Recent advances

Doraghi,

Navid,

Karimian

et al. 2024

Journal of Heterocyclic Chem

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“…3 In this direction, our group recently reported photoredox catalyzed cascade CF 3 addition/ annulation of o-alkenyl aryl ureas for the construction of 2amino-1,3-benzoxazines and dihydroquinazolinones in a chemodivergent fashion by controlling the ambident nucleophilicity of aryl ureas via selective N-versus O-cyclization. 9 However, apart from trifluoromethyl radicals, other electrophilic radicals were not viable substrates under the reaction conditions because of varied redox potentials and the reactivity of different electrophilic radical precursors (Scheme 1).…”

mentioning

confidence: 99%

“…Recently, photomediated tandem radical addition–cyclization reactions have attracted wide attention for their ability to afford functionalized molecular scaffolds in a direct fashion under mild conditions. , Although radical cascade addition followed by O-cyclization reactions are common and reported, − there are not many reports or studies on radical cascade addition and N-cyclizations of amide/urea type functional groups because of the interference of oxygen . In this direction, our group recently reported photoredox catalyzed cascade CF 3 addition/annulation of o -alkenyl aryl ureas for the construction of 2-amino-1,3-benzoxazines and dihydroquinazolinones in a chemodivergent fashion by controlling the ambident nucleophilicity of aryl ureas via selective N- versus O-cyclization . However, apart from trifluoromethyl radicals, other electrophilic radicals were not viable substrates under the reaction conditions because of varied redox potentials and the reactivity of different electrophilic radical precursors (Scheme ).…”

mentioning

confidence: 99%

Photomediated Tandem Sulfonyl Addition–Chemoselective N-Cyclization of o-Alkenyl Aryl Ureas: Direct Assembly of Functionalized Dihydroquinazolinones

Babu

Gopinath

2022

J. Org. Chem.

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Photoredox-mediated tandem addition−chemoselective cyclization of o-alkenyl aryl ureas is reported for the synthesis of sulfonyl and activated alkyl-decorated dihydroquinazolinones. By a careful choice of o-alkenyl aryl urea starting materials, we achieved chemoselective N-cyclization in the presence of more reactive amidic oxygen. We have demonstrated the scope of the methodology with a variety of sulfonyl chlorides and activated alkyl halides. Finally, large-scale synthesis of sulfonyl-substituted dihydroquinazolinone showcases the synthetic utility of the methodology.

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Selective Intermolecular Dual Amino‐Trifluoromethylation of Alkenes by High‐Valent Cu(III)−CF₃Compounds

Chen

Zhang

2022

Adv Synth Catal

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A selective intermolecular amino‐trifluoromethylation of alkenes is developed to produce a range of biologically active β‐trifluoromethyl amines. This method exploits a crucial high‐valent Cu(III)−CF3 complex as a combined source of CF3 radical and Cu(II) oxidant through homolytic Cu(III)−CF3 bond cleavage. This unique mode of CF3 radical generation is distinct from current dominant methods that rely largely on photoredox catalysis or the use of sacrificing radical initiator. This represents a significant advantage in that it greatly simplifies the reaction conditions, brings about operational convenience, and is beneficial to suppress various side reactions under otherwise more complicated conditions. A tertiary alkyl radical generated from addition of CF3 radical to alkenes is proposed to react with amines to enable C−N formation with the assistance of in‐situ Cu(II) oxidant. This reaction shows good chemo‐ and regio‐selectivity, suppressing a number of potential side reactions. The free manipulation of readily available Cu(III)−CF3 compound and feedstock compounds of alkenes and anilines greatly broadens the reaction scope. The good chemo‐ and regioselectivity, and operational convenience make this reaction attractive from the synthetic viewpoint. The reactivity of high‐valent Cu(III)−CF3 compounds disclosed in this study may be exploited to develop other interesting reactions, and to enrich the currently underdeveloped Cu(III) chemistry.

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Photoredox catalyzed cascade CF₃ addition/chemodivergent annulations of ortho-alkenyl aryl ureas

Abstract: Herein, we report a substrate-controlled cascade cyclization of o-alkenyl aryl ureas, an ambident nucleophile for constructing functionalized heterocycles such as 2-amino-1,3-benzoxazines and dihydroquinazolinones in a chemodivergent fashion using photoredox catalysis...

Cited by 8 publications

References 26 publications

2‐Vinylaniline in the synthesis of heterocycles: Recent advances

2‐Vinylaniline in the synthesis of heterocycles: Recent advances

Photomediated Tandem Sulfonyl Addition–Chemoselective N-Cyclization of o-Alkenyl Aryl Ureas: Direct Assembly of Functionalized Dihydroquinazolinones

Selective Intermolecular Dual Amino‐Trifluoromethylation of Alkenes by High‐Valent Cu(III)−CF₃Compounds

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Photoredox catalyzed cascade CF3 addition/chemodivergent annulations of ortho-alkenyl aryl ureas

Abstract: Herein, we report a substrate-controlled cascade cyclization of o-alkenyl aryl ureas, an ambident nucleophile for constructing functionalized heterocycles such as 2-amino-1,3-benzoxazines and dihydroquinazolinones in a chemodivergent fashion using photoredox catalysis...

Cited by 8 publications

References 26 publications

2‐Vinylaniline in the synthesis of heterocycles: Recent advances

2‐Vinylaniline in the synthesis of heterocycles: Recent advances

Photomediated Tandem Sulfonyl Addition–Chemoselective N-Cyclization of o-Alkenyl Aryl Ureas: Direct Assembly of Functionalized Dihydroquinazolinones

Selective Intermolecular Dual Amino‐Trifluoromethylation of Alkenes by High‐Valent Cu(III)−CF3Compounds

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Photoredox catalyzed cascade CF₃ addition/chemodivergent annulations of ortho-alkenyl aryl ureas

Selective Intermolecular Dual Amino‐Trifluoromethylation of Alkenes by High‐Valent Cu(III)−CF₃Compounds