Zinc(II)-mediated generation of 5-amino substituted 2,3-dihydro-1,2,4-oxadiazoles and their further ZnII-catalyzed and O2-involving transformations

Andrey S. Smirnov, Ekaterina S. Yandanova, Nadezhda A. Bokach, Galina L. Starova, Vladislav V. Gurzhiy, Margarita S. Avdontceva, Andrey A. Zolotarev, Vadim Yu. Kukushkin

Research output

6 Citations (Scopus)

Abstract

ZnII-activated cyanamides NCNR2 (R2 = Me2, Et2, C5H10, (CH2)2O(CH2)2, Ph2) react with the acyclic N-alkyl ketonitrones Ph2CQN+ (O)R0 (R0 = Me, CH2Ph) and N-aryl ketonitrones (R0 = Ph, p-BrC6H4, p-EtC6H4) under mild conditions. Uncomplexed 5-aminosubstituted 2,3-dihydro-1,2,4-oxadiazoles (6 examples; 49–82%) were obtained in zinc(II)-involving cycloaddition of the N-alkyl ketonitrones to the cyanamide substrates; these 2,3-dihydro-1,2,4-oxadiazoles undergo ring-opening giving carbamoylamidines and methylidenureas. The N-aryl ketonitrones react with ZnII-activated cyanamides giving the open-chain systems, viz. carbamoylamidines, N0 -(2-(diphenylmethylidene)amino)-phenyl-N,N-carbamimidic acids, and methylidenureas, which are presumably formed via the cycloaddition route followed by the N–O cleavage induced by the acceptor character of the aryl groups.
Original languageEnglish
Pages (from-to)9330–9344
Number of pages15
JournalNew Journal of Chemistry
Volume39
Issue number12
DOIs
Publication statusPublished - 2015

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Cyanamide
Oxadiazoles
Cycloaddition
Zinc
Acids
Substrates

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@article{ee33fbb1aae24770806b9bfcb9c8dd11,
title = "Zinc(II)-mediated generation of 5-amino substituted 2,3-dihydro-1,2,4-oxadiazoles and their further ZnII-catalyzed and O2-involving transformations",
abstract = "ZnII-activated cyanamides NCNR2 (R2 = Me2, Et2, C5H10, (CH2)2O(CH2)2, Ph2) react with the acyclic N-alkyl ketonitrones Ph2CQN+ (O)R0 (R0 = Me, CH2Ph) and N-aryl ketonitrones (R0 = Ph, p-BrC6H4, p-EtC6H4) under mild conditions. Uncomplexed 5-aminosubstituted 2,3-dihydro-1,2,4-oxadiazoles (6 examples; 49–82{\%}) were obtained in zinc(II)-involving cycloaddition of the N-alkyl ketonitrones to the cyanamide substrates; these 2,3-dihydro-1,2,4-oxadiazoles undergo ring-opening giving carbamoylamidines and methylidenureas. The N-aryl ketonitrones react with ZnII-activated cyanamides giving the open-chain systems, viz. carbamoylamidines, N0 -(2-(diphenylmethylidene)amino)-phenyl-N,N-carbamimidic acids, and methylidenureas, which are presumably formed via the cycloaddition route followed by the N–O cleavage induced by the acceptor character of the aryl groups.",
author = "Smirnov, {Andrey S.} and Yandanova, {Ekaterina S.} and Bokach, {Nadezhda A.} and Starova, {Galina L.} and Gurzhiy, {Vladislav V.} and Avdontceva, {Margarita S.} and Zolotarev, {Andrey A.} and Kukushkin, {Vadim Yu.}",
year = "2015",
doi = "10.1039/c5nj02061a",
language = "English",
volume = "39",
pages = "9330–9344",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "12",

}

TY - JOUR

T1 - Zinc(II)-mediated generation of 5-amino substituted 2,3-dihydro-1,2,4-oxadiazoles and their further ZnII-catalyzed and O2-involving transformations

AU - Smirnov, Andrey S.

AU - Yandanova, Ekaterina S.

AU - Bokach, Nadezhda A.

AU - Starova, Galina L.

AU - Gurzhiy, Vladislav V.

AU - Avdontceva, Margarita S.

AU - Zolotarev, Andrey A.

AU - Kukushkin, Vadim Yu.

PY - 2015

Y1 - 2015

N2 - ZnII-activated cyanamides NCNR2 (R2 = Me2, Et2, C5H10, (CH2)2O(CH2)2, Ph2) react with the acyclic N-alkyl ketonitrones Ph2CQN+ (O)R0 (R0 = Me, CH2Ph) and N-aryl ketonitrones (R0 = Ph, p-BrC6H4, p-EtC6H4) under mild conditions. Uncomplexed 5-aminosubstituted 2,3-dihydro-1,2,4-oxadiazoles (6 examples; 49–82%) were obtained in zinc(II)-involving cycloaddition of the N-alkyl ketonitrones to the cyanamide substrates; these 2,3-dihydro-1,2,4-oxadiazoles undergo ring-opening giving carbamoylamidines and methylidenureas. The N-aryl ketonitrones react with ZnII-activated cyanamides giving the open-chain systems, viz. carbamoylamidines, N0 -(2-(diphenylmethylidene)amino)-phenyl-N,N-carbamimidic acids, and methylidenureas, which are presumably formed via the cycloaddition route followed by the N–O cleavage induced by the acceptor character of the aryl groups.

AB - ZnII-activated cyanamides NCNR2 (R2 = Me2, Et2, C5H10, (CH2)2O(CH2)2, Ph2) react with the acyclic N-alkyl ketonitrones Ph2CQN+ (O)R0 (R0 = Me, CH2Ph) and N-aryl ketonitrones (R0 = Ph, p-BrC6H4, p-EtC6H4) under mild conditions. Uncomplexed 5-aminosubstituted 2,3-dihydro-1,2,4-oxadiazoles (6 examples; 49–82%) were obtained in zinc(II)-involving cycloaddition of the N-alkyl ketonitrones to the cyanamide substrates; these 2,3-dihydro-1,2,4-oxadiazoles undergo ring-opening giving carbamoylamidines and methylidenureas. The N-aryl ketonitrones react with ZnII-activated cyanamides giving the open-chain systems, viz. carbamoylamidines, N0 -(2-(diphenylmethylidene)amino)-phenyl-N,N-carbamimidic acids, and methylidenureas, which are presumably formed via the cycloaddition route followed by the N–O cleavage induced by the acceptor character of the aryl groups.

U2 - 10.1039/c5nj02061a

DO - 10.1039/c5nj02061a

M3 - Article

VL - 39

SP - 9330

EP - 9344

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 12

ER -