Synthesis of methylene-bridged α,β-unsaturated ketones: α-Csp3–H methylenation of aromatic ketones using Selectfluor as a mild oxidant

Zhang, Yuan; Zhi-qi, Liu; Zhu, Tong; Huang, Yongjie; Fan, Weibin; Huang, Deguang

doi:10.1039/d1ob02043a

Cited by 3 publications

(1 citation statement)

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“…Selectfluor is an efficient oxidant and/or radical initiator in organic synthesis ( Galloway et al, 2017 ; Gao et al, 2018 ; Hu et al, 2019 ; Niu et al, 2019 ). We have used it as an oxidant for the generation of methylene groups via C–N/C–O bond break ( Jin et al, 2021 ; Zhang et al, 2022 ). Herein, we report a facile and efficient method for the preparation of 4-aminoisophthalaldehyde, in which DMSO, Cu(OTf) 2 , and Selectfluor were used as the formyl source, catalyst and radical initiator, respectively Scheme 2F .…”

Section: Introductionmentioning

confidence: 99%

Copper(II)-Catalyzed Selective CAr-H Bond Formylation: Synthesis of Dialdehyde Aniline

Guo

Fan

et al. 2022

Front. Chem.

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A simple and efficient method for the synthesis of dialdehyde aniline in good yields (up to 83%) is explored using Cu(OTf)2 as the catalyst, Selectfluor as the radical initiator, and DMSO as both the carbon and oxygen sources. Experimental studies indicate that the reaction is achieved by the formylation of two CAr-H bonds, first at the para-position and then at the ortho-position. A possible mechanism is proposed, including the thermal homolysis of Selectfluor, the Cu(II)-facilitated formylation of the CAr-H bonds, and the hydrolysis of the amide under alkaline conditions in air atmosphere.

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Section: Introductionmentioning

confidence: 99%

Copper(II)-Catalyzed Selective CAr-H Bond Formylation: Synthesis of Dialdehyde Aniline

Guo

Fan

et al. 2022

Front. Chem.

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Substrate‐induced Selective α‐C(sp³)−H Activation of N‐alkyl Amines: Synthesis of Coumarin‐fused Quinolinones under Air

Zhang,

Wan,

Yin

et al. 2024

Adv Synth Catal

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A substrate‐induced synthesis of coumarin‐fused quinolinones is achieved from 4‐(phenylamino)‐2H‐chromen‐2‐ones using N‐alkyl amines as the solvent and a carbon source under air conditions without any catalysts in one pot. This protocol highlights the special roles of 4‐(phenylamino)‐2H‐chromen‐2‐ones which were not only used as reactants but also as an internal oxidant selectively activated N‐α‐C(sp3)–H bond. This reaction features catalyst‐free, broad substrate scopes (N‐alkyl amines 27 examples and quinolinones 24 examples), operationally simple for the one‐step synthesis, and recovery and recycling of the solvent.

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Selectfluor-promoted α-methylenation of aromatic ketones to terminal olefins using acetonitrile as one carbon source

Liu

Zhang

Fan

et al. 2022

Tetrahedron Letters

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Synthesis of methylene-bridged α,β-unsaturated ketones: α-C_sp³–H methylenation of aromatic ketones using Selectfluor as a mild oxidant

Abstract: A three starting materials four components reaction (3SM-4CR) is developed for the synthesis of α,β-unsaturated ketones and β-amino ketones in good yields. The reaction employs tetramethylethylenediamine (TMEDA) as a methylene...

Cited by 3 publications

References 51 publications

Copper(II)-Catalyzed Selective CAr-H Bond Formylation: Synthesis of Dialdehyde Aniline

Copper(II)-Catalyzed Selective CAr-H Bond Formylation: Synthesis of Dialdehyde Aniline

Substrate‐induced Selective α‐C(sp³)−H Activation of N‐alkyl Amines: Synthesis of Coumarin‐fused Quinolinones under Air

Selectfluor-promoted α-methylenation of aromatic ketones to terminal olefins using acetonitrile as one carbon source

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Synthesis of methylene-bridged α,β-unsaturated ketones: α-Csp3–H methylenation of aromatic ketones using Selectfluor as a mild oxidant

Abstract: A three starting materials four components reaction (3SM-4CR) is developed for the synthesis of α,β-unsaturated ketones and β-amino ketones in good yields. The reaction employs tetramethylethylenediamine (TMEDA) as a methylene...

Cited by 3 publications

References 51 publications

Copper(II)-Catalyzed Selective CAr-H Bond Formylation: Synthesis of Dialdehyde Aniline

Copper(II)-Catalyzed Selective CAr-H Bond Formylation: Synthesis of Dialdehyde Aniline

Substrate‐induced Selective α‐C(sp3)−H Activation of N‐alkyl Amines: Synthesis of Coumarin‐fused Quinolinones under Air

Selectfluor-promoted α-methylenation of aromatic ketones to terminal olefins using acetonitrile as one carbon source

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Synthesis of methylene-bridged α,β-unsaturated ketones: α-C_sp³–H methylenation of aromatic ketones using Selectfluor as a mild oxidant

Substrate‐induced Selective α‐C(sp³)−H Activation of N‐alkyl Amines: Synthesis of Coumarin‐fused Quinolinones under Air