EventsThe 21st International Electronic Conference on Synthetic Organic Chemistry
Event submissions
Published
with-doi10.3390/ecsoc-21-04766
This submission belongs to the session E. Computational Chemistry of the event The 21st International Electronic Conference on Synthetic Organic Chemistry
Published date
03 Nov, 2017
Citation
Anatoly Shutalev, Anastasia Fesenko, Ring Expansion Tetrahydropyrimidin-2-ones into Tetrahydro-1H-1,3-diazepin-2-ones: a Theoretical Study, in Proceedings of The 21st International Electronic Conference on Synthetic Organic Chemistry, 1 November–30 November 2017, MDPI: Basel, Switzerland, doi: 10.3390/ecsoc-21-04766
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Ring Expansion Tetrahydropyrimidin-2-ones into Tetrahydro-1H-1,3-diazepin-2-ones: a Theoretical Study

Anatoly Shutalev 1
Anastasia Fesenko 1
1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., 119991 Moscow, Russian Federation
Abstract

A plausible mechanism for the nucleophile-mediated ring expansion of 4-chloromethyl-1,2,3,4-tetrahydropyrimidin-2-ones into 2,3,6,7-tetrahydro-1H-1,3-diazepin-2-ones based on DFT calculations at B3LYP/6-31+G(d,p) level is discussed. This mechanism involves the following subsequent steps: N(1)H deprotonation under the action of nucleophile, intramolecular nucleophilic substitution of the chlorine atom to give cyclopropane bicyclic intermediate, nucleophile-promoted cyclopropane ring opening leading to 2,5-dihydro-1H-1,3-diazepin-2-one, and addition of nucleophiles to the C=N bond to afford the final diazepinones.

Keywords
Tetrahydropyrimidin-2-ones
Tetrahydro-1H-1,3-diazepin-2-ones
Ring expansion
Nucleophiles
DFT calculations
Reaction mechanism
Manuscript
Proceedings_Pyrimidine-Diazepine Ring Expansion.pdf
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