Water-Tuned Tautomer-Selective Tandem Synthesis of the 5,6-Dihydropyrimidin-4(3 H )-ones, Driven under the Umbrella of Sustainable Chemistry
Само за регистроване кориснике
2018
Аутори
Janković, Nenad Ž.Stefanović, Srđan M.
Petronijević, Jelena
Joksimović, Nenad
Novaković, Slađana B.
Bogdanović, Goran A.
Muškinja, Jovana
Vraneš, Milan
Ratković, Zoran R.
Bugarčić, Zorica M.
Чланак у часопису (Објављена верзија)
,
© Copyright 2018 American Chemical Society
Метаподаци
Приказ свих података о документуАпстракт
The selective synthesis of 5,6-dihydropyrimidin-4(3H)-one scaffold (precursor of dihydrouracil) was a very difficult synthetic challenge that, so far, has not been achieved. For the first time, in this paper, green, selective and high-yields approach to 40 novel 5,6-dihydropyrimidin-4(3H)-ones (DHPMs) by one-pot reaction of aldehydes, Meldrum's acid and isothioureas under solvent-free conditions, in the presence of water, since an additive is presented. In the majority of cases, introduced methodology gave an unprecedented tautomer-selective fashion toward targeted compounds with excellent tautomeric purity (>99.9%), which reached 100% in few cases. The molecular structure of the five compounds has been determined by X-ray crystallography. In each one of them, very short length for the corresponding N2-C1 bond was noticed, making them especially interesting from a structural standpoint. This experimental fact can imply a highly localized electron π density in this part of each heterocy...clic ring. The obtained experimental results, which are determined from NMR and ESI-MS study, indicate that this Biginelli-type reaction smoothly proceeds in a one-pot mode, pointing to the three-step tandem process, proceeding via the Knoevenagel, aza-Michael, and retro-Diels-Alder reactions. The presented strategy also had the following advantages: reduction amount of waste, excellent values of green chemistry metrics (cEF, EcoScale and GCIS), and it is the first eco-friendly strategy toward the DHPMs scaffold. © Copyright 2018 American Chemical Society.
Кључне речи:
Biginelli-Atwal reaction / solvent-free / dihydrouracil / diazoles / tautomer-selective / short C=N bond / green metricsИзвор:
ACS Sustainable Chemistry and Engineering, 2018, 6, 10, 13358-13366Финансирање / пројекти:
- Испитивање механизма реакција комплекса јона прелазних метала са биолошки значајним молекулима (RS-MESTD-Basic Research (BR or ON)-172011)
- Нове електрохемијске и хемијске методе у синтези органских једињења од интереса за медицину и хемију материјала (RS-MESTD-Basic Research (BR or ON)-172034)
Напомена:
- Supporting data: http://vinar.vin.bg.ac.rs/handle/123456789/7888
DOI: 10.1021/acssuschemeng.8b03127
ISSN: 2168-0485
WoS: 000446413100084
Scopus: 2-s2.0-85053342893
URI
http://pubs.acs.org/doi/10.1021/acssuschemeng.8b03127https://vinar.vin.bg.ac.rs/handle/123456789/7886
Колекције
Институција/група
VinčaTY - JOUR AU - Janković, Nenad Ž. AU - Stefanović, Srđan M. AU - Petronijević, Jelena AU - Joksimović, Nenad AU - Novaković, Slađana B. AU - Bogdanović, Goran A. AU - Muškinja, Jovana AU - Vraneš, Milan AU - Ratković, Zoran R. AU - Bugarčić, Zorica M. PY - 2018 UR - http://pubs.acs.org/doi/10.1021/acssuschemeng.8b03127 UR - https://vinar.vin.bg.ac.rs/handle/123456789/7886 AB - The selective synthesis of 5,6-dihydropyrimidin-4(3H)-one scaffold (precursor of dihydrouracil) was a very difficult synthetic challenge that, so far, has not been achieved. For the first time, in this paper, green, selective and high-yields approach to 40 novel 5,6-dihydropyrimidin-4(3H)-ones (DHPMs) by one-pot reaction of aldehydes, Meldrum's acid and isothioureas under solvent-free conditions, in the presence of water, since an additive is presented. In the majority of cases, introduced methodology gave an unprecedented tautomer-selective fashion toward targeted compounds with excellent tautomeric purity (>99.9%), which reached 100% in few cases. The molecular structure of the five compounds has been determined by X-ray crystallography. In each one of them, very short length for the corresponding N2-C1 bond was noticed, making them especially interesting from a structural standpoint. This experimental fact can imply a highly localized electron π density in this part of each heterocyclic ring. The obtained experimental results, which are determined from NMR and ESI-MS study, indicate that this Biginelli-type reaction smoothly proceeds in a one-pot mode, pointing to the three-step tandem process, proceeding via the Knoevenagel, aza-Michael, and retro-Diels-Alder reactions. The presented strategy also had the following advantages: reduction amount of waste, excellent values of green chemistry metrics (cEF, EcoScale and GCIS), and it is the first eco-friendly strategy toward the DHPMs scaffold. © Copyright 2018 American Chemical Society. T2 - ACS Sustainable Chemistry and Engineering T1 - Water-Tuned Tautomer-Selective Tandem Synthesis of the 5,6-Dihydropyrimidin-4(3 H )-ones, Driven under the Umbrella of Sustainable Chemistry VL - 6 IS - 10 SP - 13358 EP - 13366 DO - 10.1021/acssuschemeng.8b03127 ER -
@article{ author = "Janković, Nenad Ž. and Stefanović, Srđan M. and Petronijević, Jelena and Joksimović, Nenad and Novaković, Slađana B. and Bogdanović, Goran A. and Muškinja, Jovana and Vraneš, Milan and Ratković, Zoran R. and Bugarčić, Zorica M.", year = "2018", abstract = "The selective synthesis of 5,6-dihydropyrimidin-4(3H)-one scaffold (precursor of dihydrouracil) was a very difficult synthetic challenge that, so far, has not been achieved. For the first time, in this paper, green, selective and high-yields approach to 40 novel 5,6-dihydropyrimidin-4(3H)-ones (DHPMs) by one-pot reaction of aldehydes, Meldrum's acid and isothioureas under solvent-free conditions, in the presence of water, since an additive is presented. In the majority of cases, introduced methodology gave an unprecedented tautomer-selective fashion toward targeted compounds with excellent tautomeric purity (>99.9%), which reached 100% in few cases. The molecular structure of the five compounds has been determined by X-ray crystallography. In each one of them, very short length for the corresponding N2-C1 bond was noticed, making them especially interesting from a structural standpoint. This experimental fact can imply a highly localized electron π density in this part of each heterocyclic ring. The obtained experimental results, which are determined from NMR and ESI-MS study, indicate that this Biginelli-type reaction smoothly proceeds in a one-pot mode, pointing to the three-step tandem process, proceeding via the Knoevenagel, aza-Michael, and retro-Diels-Alder reactions. The presented strategy also had the following advantages: reduction amount of waste, excellent values of green chemistry metrics (cEF, EcoScale and GCIS), and it is the first eco-friendly strategy toward the DHPMs scaffold. © Copyright 2018 American Chemical Society.", journal = "ACS Sustainable Chemistry and Engineering", title = "Water-Tuned Tautomer-Selective Tandem Synthesis of the 5,6-Dihydropyrimidin-4(3 H )-ones, Driven under the Umbrella of Sustainable Chemistry", volume = "6", number = "10", pages = "13358-13366", doi = "10.1021/acssuschemeng.8b03127" }
Janković, N. Ž., Stefanović, S. M., Petronijević, J., Joksimović, N., Novaković, S. B., Bogdanović, G. A., Muškinja, J., Vraneš, M., Ratković, Z. R.,& Bugarčić, Z. M.. (2018). Water-Tuned Tautomer-Selective Tandem Synthesis of the 5,6-Dihydropyrimidin-4(3 H )-ones, Driven under the Umbrella of Sustainable Chemistry. in ACS Sustainable Chemistry and Engineering, 6(10), 13358-13366. https://doi.org/10.1021/acssuschemeng.8b03127
Janković NŽ, Stefanović SM, Petronijević J, Joksimović N, Novaković SB, Bogdanović GA, Muškinja J, Vraneš M, Ratković ZR, Bugarčić ZM. Water-Tuned Tautomer-Selective Tandem Synthesis of the 5,6-Dihydropyrimidin-4(3 H )-ones, Driven under the Umbrella of Sustainable Chemistry. in ACS Sustainable Chemistry and Engineering. 2018;6(10):13358-13366. doi:10.1021/acssuschemeng.8b03127 .
Janković, Nenad Ž., Stefanović, Srđan M., Petronijević, Jelena, Joksimović, Nenad, Novaković, Slađana B., Bogdanović, Goran A., Muškinja, Jovana, Vraneš, Milan, Ratković, Zoran R., Bugarčić, Zorica M., "Water-Tuned Tautomer-Selective Tandem Synthesis of the 5,6-Dihydropyrimidin-4(3 H )-ones, Driven under the Umbrella of Sustainable Chemistry" in ACS Sustainable Chemistry and Engineering, 6, no. 10 (2018):13358-13366, https://doi.org/10.1021/acssuschemeng.8b03127 . .