Ni-Catalyzed C–H Cyanation of (Hetero)arenes with 2-Cyanoisothiazolidine 1,1-Dioxide as a Cyanation Reagent

Ma, Junjie; Líu, Hao; He, Xin; Chen, Zhicheng; Liu, Yue; Hou, Chuanfu; Sun, Zheng; Chu, W. K.

doi:10.1021/acs.orglett.1c00468

Cited by 8 publications

(3 citation statements)

References 33 publications

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“…Nitriles are important intermediates in organic synthesis and a crucial moiety with a wide application in medicinal, organic, and polymer chemistry. , General methods for synthesizing nitriles mainly include the nucleophilic cyanation of alkyl halides, Wittig reactions, and transition-metal-catalyzed cyanation of arenes. , However, these methods demonstrate the drawbacks associated with using high-cost starting materials, the generation of toxic wastes, and the poor atomic efficiency. Therefore, much effort has been devoted to developing novel catalytic methods for the environmentally friendly synthesis of nitriles.…”

Section: Introductionmentioning

confidence: 99%

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating ^•O₂^– and Br^• Radicals over Iron-Modified TiO₂ Photocatalysts

Xian

et al. 2022

J. Am. Chem. Soc.

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Catalytic ammoxidation of alcohols into nitriles is an essential reaction in organic synthesis. While highly desirable, conducting the synthesis at room temperature is challenging, using NH 3 as the nitrogen source, O 2 as the oxidant, and a catalyst without noble metals. Herein, we report robust photocatalysts consisting of Fe(III)-modified titanium dioxide (Fe/TiO 2 ) for ammoxidation reactions at room temperature utilizing oxygen at atmospheric pressure, NH 3 as the nitrogen source, and NH 4 Br as an additive. To the best of our knowledge, this is the first example of catalytic ammoxidation of alcohols over a photocatalyst using such cheap and benign materials. Various (hetero) aromatic nitriles were synthesized at high yields, and aliphatic alcohols could also be transformed into corresponding nitriles at considerable yields. The modification of TiO 2 with Fe(III) facilitates the formation of active • O 2 − radicals and increases the adsorption of NH 3 and amino intermediates on the catalyst, accelerating the ammoxidation to yield nitriles. The additive NH 4 Br impressively improves the catalytic efficiency via the formation of bromine radicals (Br • ) from Br − , which works synergistically with • O 2 − to capture H • from C α -H, which is present in benzyl alcohol and the intermediate aldimine (RCH�NH), to generate the active carbon-centered radicals. Further, the generation of Br • from the Br − additive consumes the photogenerated holes and OH • radicals to prevent over-oxidation, significantly improving the selectivity toward nitriles. This amalgamation of function and synergy of the Fe(III)-doped TiO 2 and NH 4 Br reveals new opportunities for developing semiconductor-based photocatalytic systems for fine chemical synthesis.

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Section: Introductionmentioning

confidence: 99%

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating ^•O₂^– and Br^• Radicals over Iron-Modified TiO₂ Photocatalysts

Xian

et al. 2022

J. Am. Chem. Soc.

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“…In 2021, our group reported a Ni(II)-catalyzed method by using NCITD as the cyano source. 7 The groups of Glorius, Chang, and Ackermann, separately, reported Co(III)-catalyzed methods by using Ncyanosuccinimide or NCTS as the cyano source. 8 Although these strategies have made good progress, they have defects of harsh reaction conditions (more than 100 °C) and unrecoverable solvent (Scheme 1b).…”

mentioning

confidence: 99%

“…In order to overcome these problems, in recent years, different organic compounds containing a cyano moiety have been successfully used as effective cyano sources for the transition-metal-catalyzed direct cyanation reaction of a C–H bond. In 2021, our group reported a Ni(II)-catalyzed method by using NCITD as the cyano source . The groups of Glorius, Chang, and Ackermann, separately, reported Co(III)-catalyzed methods by using N -cyanosuccinimide or NCTS as the cyano source .…”

mentioning

confidence: 99%

N-Cyano-2,2′-biphenyldicarboimide as a Cyanation Reagent for Co(III)-Catalyzed C–H Cyanation of Indoles in Ionic Liquids

et al. 2023

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A mild strategy for Co(III)-catalyzed C(sp2)–H cyanation of indoles was developed by using NCBLD as an electrophilic cyanation reagent and 1-butyl-3-acetylimidazole ditrifluoromethylsulfonimide ([BAIM]NTf2) as an environmentally friendly and recyclable solvent, and a series of 2-cyano products were obtained at room temperature. Adopting this strategy, the unnatural nucleotide fragment precursor of Remdesivir, which was a drug for COVID-19, was synthesized through cyano transformation, further proving the practicability of this cyanation method.

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Cu₂O‐Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion

Liu

Tang

Zheng

et al. 2021

Chemistry An Asian Journal

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Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu2O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3‐phenylacrylonitrile.

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Ni-Catalyzed C–H Cyanation of (Hetero)arenes with 2-Cyanoisothiazolidine 1,1-Dioxide as a Cyanation Reagent

Cited by 8 publications

References 33 publications

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating ^•O₂^– and Br^• Radicals over Iron-Modified TiO₂ Photocatalysts

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating ^•O₂^– and Br^• Radicals over Iron-Modified TiO₂ Photocatalysts

N-Cyano-2,2′-biphenyldicarboimide as a Cyanation Reagent for Co(III)-Catalyzed C–H Cyanation of Indoles in Ionic Liquids

Cu₂O‐Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion

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Ni-Catalyzed C–H Cyanation of (Hetero)arenes with 2-Cyanoisothiazolidine 1,1-Dioxide as a Cyanation Reagent

Cited by 8 publications

References 33 publications

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating •O2– and Br• Radicals over Iron-Modified TiO2 Photocatalysts

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating •O2– and Br• Radicals over Iron-Modified TiO2 Photocatalysts

N-Cyano-2,2′-biphenyldicarboimide as a Cyanation Reagent for Co(III)-Catalyzed C–H Cyanation of Indoles in Ionic Liquids

Cu2O‐Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion

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High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating ^•O₂^– and Br^• Radicals over Iron-Modified TiO₂ Photocatalysts

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating ^•O₂^– and Br^• Radicals over Iron-Modified TiO₂ Photocatalysts

Cu₂O‐Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion