Synthesis of nitromethyl-, N-methylindolyl-, or N-methylindolylnitromethyl-substituted 1,4-benzothiazin(diazin)ones and 3-methyl-1,4-benzoxazinones from alkyl 3-nitroacrylates

Pelipko, V. V.; Байчурин, Р. И.; Kustin, R. P.; Vinogradov, Alexander P.; Makarenko, S. V.

doi:10.1007/s10593-018-2339-2

Cited by 6 publications

(4 citation statements)

References 39 publications

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“…In all cases, the reaction proceeded through the initial formation of aza‐Michael adduct 76 followed by the intramolecular cyclization with participation of second nucleophilic center and ester group. Thus, even the creation of a sterically hindered electrophilic center does not switch the direction of the nucleophilic attack: the reactivity of such Michael acceptors is mainly determined by the nitro group [80] …”

Section: Aza‐michael Reaction With Pull‐pull Enoatesmentioning

confidence: 99%

“…Thus, even the creation of a sterically hindered electrophilic center does not switch the direction of the nucleophilic attack: the reactivity of such Michael acceptors is mainly determined by the nitro group. [80] Incorporation of the halogen into the β-position of initial β-nitroenoate changed the reaction pathway. [81,82] As expected, in the first step β-halo-β-nitroarcylates 79 added secondary aliphatic or primary aromatic amines to give the aza-Michael adduct 80.…”

Section: Conjugate Nucleophilic Addition To β-Nitroenoatesmentioning

confidence: 99%

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Pull‐Pull Alkenes in the Aza‐Michael Reaction

Rulev

Tyumentsev

2022

Adv Synth Catal

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Aza‐Michael addition is known to be one of the most exploited reactions in organic chemistry. Taking into account the fact that each seventh reaction in pharmaceutical industry involves the formation of at least one C−N bond, it is not surprising that this reaction is especially valuable for the synthesis of bioactive compounds and drugs. Traditionally, only push‐pull alkenes are regarded as starting material for this reaction. The participation of pull‐pull alkenes as Michael acceptors is much less studied. The presence of two vicinal electron‐withdrawing groups makes them highly reactive in nucleophilic reactions especially with nitrogen‐centered nucleophiles. This feature allows them to be excellent building blocks in the synthesis of bioactive molecules and polyfunctional materials. The review considers the most important and sometimes unexpected results obtained over the last two decades on the conjugate addition of nitrogen nucleophiles to pull‐pull alkenes bearing various acceptor moieties (alkoxycarbonyl‐, carbonyl‐, formyl‐, cyano‐, trifluoromethyl‐ or nitro group) in various combinations.

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Section: Aza‐michael Reaction With Pull‐pull Enoatesmentioning

confidence: 99%

Section: Conjugate Nucleophilic Addition To β-Nitroenoatesmentioning

confidence: 99%

Pull‐Pull Alkenes in the Aza‐Michael Reaction

Rulev

Tyumentsev

2022

Adv Synth Catal

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“…[1][2][3] One of the important features of their chemical behavior is an attack of carbon-and heteroatom-(O, N, S) centered nucleophiles onto the carbon C 2 of β-nitroacrylates (β-position relatively to nitro group, and αposition to ester one) due to stronger electron withdrawing character of NO 2 substituent. [4][5][6][7] Generally, conjugated nitroalkenes being electron deficient compounds act as dienophiles in the Diels-Alder reaction, dipoles in [3 + 2] cycloaddition, [8] acceptors in the Michael reaction, or react with C, N, O, S-centered nucleophiles. [9] These reactions can be conducted in an asymmetric way.…”

Section: Introductionmentioning

confidence: 99%

“…Chemical transformations of these compounds allow obtaining various functional derivatives, carbo‐ and heterocycles, and many other substances including biologically active substrates [1–3] . One of the important features of their chemical behavior is an attack of carbon‐ and heteroatom‐(O, N, S) centered nucleophiles onto the carbon C 2 of β‐nitroacrylates (β‐position relatively to nitro group, and α‐position to ester one) due to stronger electron withdrawing character of NO 2 substituent [4–7] …”

Section: Introductionmentioning

confidence: 99%

Reactions of Alkyl β‐Nitroacrylates with Arenes in Triflic Acid: Synthesis of Oximes of Alkyl 2,3‐Diaryl‐3‐oxopropanoates

Zhelonkina,

Khoroshilova,

Ivanov

et al. 2023

ChemistrySelect

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Methyl or ethyl 3‐nitropropenoates (β‐nitroacrylates) AlkO(O)C1−C2H=C3H−NO2 in reaction with arenes ArH in triflic acid CF3SO3H (TfOH) at room temperature in 1 h give rise to oximes of alkyl 2,3‐diaryl‐3‐oxopropanoates AlkO(O)C−CH(Ar)−C(Ar)=NOH in yields of 42–92 %. The obtained oximes bearing ortho‐methyl substituents in the aryl ring exist as atropoisomers in solutions. The study of protonated forms of β‐nitroacrylates by NMR and DFT calculations has revealed that the reactive electrophiles are species AlkO(HO+)C1−C2H=C3H−N+(O)(OH) protosolvated on the acceptor groups NO2 and CO2R. Plausible reaction mechanism is based on the primary interaction of aromatic nucleophiles with these electrophilic species onto their carbon C2.

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Synthesis of Heterocyclic Systems Starting from Carbonyl and Carboxyl Functionalized Nitro Compounds by One‐Pot Processes

Palmieri

2020

Eur J Org Chem

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One‐pot processes are nowadays considered as one of the main synthetic approaches aimed to minimize the waste production and the energy consumption according to the green chemistry principles. In particular, the use of easily accessible polyfunctionalized starting materials permits the preparation of complex targets in very straightforward and simple ways. In this review, uses of carbonyl and carboxyl functionalized nitro derivatives, such as β‐nitro acrylates, β‐nitro enones, and protected β‐nitro ketones, as profitable building blocks of the most important nitrogen, oxygen and sulfur containing heterocyclic systems are summarized.

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Synthesis of nitromethyl-, N-methylindolyl-, or N-methylindolylnitromethyl-substituted 1,4-benzothiazin(diazin)ones and 3-methyl-1,4-benzoxazinones from alkyl 3-nitroacrylates

Cited by 6 publications

References 39 publications

Pull‐Pull Alkenes in the Aza‐Michael Reaction

Pull‐Pull Alkenes in the Aza‐Michael Reaction

Reactions of Alkyl β‐Nitroacrylates with Arenes in Triflic Acid: Synthesis of Oximes of Alkyl 2,3‐Diaryl‐3‐oxopropanoates

Synthesis of Heterocyclic Systems Starting from Carbonyl and Carboxyl Functionalized Nitro Compounds by One‐Pot Processes

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