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Review
. 2020 Feb 11:8:77.
doi: 10.3389/fchem.2020.00077. eCollection 2020.

Electrophilically Activated Nitroalkanes in Reactions With Carbon Based Nucleophiles

Nicolai A Aksenov  1 , Alexander V Aksenov  1 , Sergei N Ovcharov  1 , Dmitrii A Aksenov  1 , Michael Rubin  1   2
Affiliations
Review

Electrophilically Activated Nitroalkanes in Reactions With Carbon Based Nucleophiles

Nicolai A Aksenov et al. Front Chem. .

Abstract

Unusual reactivity of nitroalkanes, involving formation of aci-forms (nitronic acids or nitronates) and their subsequent interaction with carbon-based nucleophiles, is surveyed in this review.

Keywords: C-H functionalization; electrophilic attack; nitroalkanes; oximes; synthetic methodology.

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Figures

Scheme 1
Scheme 1
Reactions of electrophilically activated nitroalkanes with Vilsmeier reagent.
Scheme 2
Scheme 2
Alpha-activation of nitroalkanes toward reaction with electron-rich arenes.
Scheme 3
Scheme 3
Beta-activation of nitroalkanes toward reaction with electron-rich arenes.
Scheme 4
Scheme 4
Reaction of trihalogenmethylated nitro-olefins.
Scheme 5
Scheme 5
Employment of TFSA to produce aci-form of nitroalkanes.
Scheme 6
Scheme 6
Reactivity of 1,1-bis(methylthio)-2-nitroethylene.
Scheme 7
Scheme 7
Reactions of nitroalkanes with arenes under conditions of Frieden-Crafts reaction.
Scheme 8
Scheme 8
Reactions of primary nitroalkanes with arenes in polyphosphoric acid.
Scheme 9
Scheme 9
Reactions of nitromethane and secondary nitroalkanes with arenes in polyphosphoric acid.
Scheme 10
Scheme 10
Cyclizations of nitroalkanes involving intramolecular reactions with electron-rich arenes.
Scheme 11
Scheme 11
Cyclization involving 1,1-bis(methylthio)-2-nitroethylene.
Scheme 12
Scheme 12
Vicarious substitution off involving electrophilic mitroalkanes.
Scheme 13
Scheme 13
Alpha-alkylations of cyclic nitronates.
Scheme 14
Scheme 14
Beta-cyanation of cyclic nitronates.
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References

    1. Aksenov A. V., Aksenov N. A., Nadein O. N., Aksenova I. V. (2010). Nitroethane in polyphosphoric acid: a new reagent for acetamidation and amination of aromatic compounds. Synlett 2628–2630. 10.1055/s-0030-1258767 - DOI
    1. Aksenov A. V., Aksenov N. A., Nadein O. N., Aksenova I. V. (2012). Nitromethane in polyphosphoric acid - a new reagent for carboxyamidation and carboxylation of activated aromatic compounds. Synth. Commun. 42, 541–547. 10.1080/00397911.2010.526284 - DOI
    1. Aksenov A. V., Aksenov N. A., Orazova N. A., Aksenov D. A., Dmitriev M. V., Rubin M. (2015). Direct metal-free synthesis of diarylamines from 2-nitropropane via the twofold C-H functionalization of arenes. RSC Adv. 5, 84849–84855. 10.1039/C5RA17668A - DOI
    1. Aksenov A. V., Aksenov N. A., Ovcharov D. S., Aksenov D. A., Griaznov G., Voskressensky L. G., et al. (2016). Rational design of an efficient one-pot synthesis of 6H-pyrrolo[2,3,4-gh] perimidines in polyphosphoric acid. RSC Adv. 6, 82425–82431. 10.1039/C6RA17269E - DOI
    1. Aksenov N. A., Aksenov A. V., Nadein O. N., Aksenov D. A., Smirnov A. N., Rubin M. (2015). One-pot synthesis of benzoxazoles via the metal-free ortho-C-H functionalization of phenols with nitroalkanes. RSC Adv. 5, 71620–71626. 10.1039/C5RA15128G - DOI

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