Inverse Electron Demand Diels-Alder Reaction of Pyrazines with 2,5-Norbornadiene as Acetylene Precursor

Inverse Electron Demand Diels-Alder Reaction of Pyrazines with 2,5-Norbornadiene as Acetylene Precursor Научная публикация

Журнал

Synthesis
ISSN: 1437-210X , E-ISSN: 0039-7881

Вых. Данные

Год: 2025, Том: 57, Номер: 04, Страницы: 812-819 Страниц : 8 DOI: 10.1055/a-2495-3296

Авторы

Krinochkin Alexey P. ¹ , Savchuk Maria I ¹ , Kudryashova Ekaterina A. ¹ , Potapova Svetlana S. ¹ , Potapova Anastasia ¹ , Fatykhov Ramil ¹ , Khalymbadzha Igor A ¹ , Sharapov Ainur ¹ , Kopchuk Dmitry Sergeevich ¹ , Kovalev Igor S. ¹ , Petrova Victoria E. ¹ , Krivoshchapov Nikolai V. ² , Zyryanov Grigory V. ¹

Организации

1	Organic and biomolecular chemistry, Ural Federal University named after the first President of Russia B N Yeltsin, Ekaterinburg, Russian Federation
2	Theoretical Chemistry (No. 24), FSBIS N D Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Moskva, Russian Federation

Herein, we report the reaction of pyrazines with 2,5-norbornadiene, an acetylene precursor, as a cascade of Diels-Alder reactions yielding substituted pyridines. In contrast to the known examples of intermolecular Diels-Alder type reaction of pyrazines with acetylene, which usually leads to a mixture of products, in our case the formation of a single isomer was observed. The proposed approach allows the conversion of pyrazines with different types of substitution, except those containing methyl and amino donor groups, to pyridines. In addition, highly functionalized aminonicotic esters were obtained, which can be used for the synthesis of bioactive compounds. An unusual course of the Diels-Alder reaction was found in the case of tetrasubstituted pyrazines, which cleave organic nitriles instead of HCN. Quantum-chemical modeling of possible transition states showed that this Diels-Alder reaction proceeds via cycloaddition of 2,5-norbornadiene to pyrazine with sequential elimination of HCN and cyclopentadene; the reaction pathway including initial formation of acetylene from norbornadiene and subsequent Diels-Alder reaction with the acetylene was rejected as kinetically unfavorable.

Krinochkin A.P. , Savchuk M.I. , Kudryashova E.A. , Potapova S.S. , Potapova A. , Fatykhov R. , Khalymbadzha I.A. , Sharapov A. , Kopchuk D.S. , Kovalev I.S. , Petrova V.E. , Krivoshchapov N.V. , Zyryanov G.V.
Inverse Electron Demand Diels-Alder Reaction of Pyrazines with 2,5-Norbornadiene as Acetylene Precursor
Synthesis. 2025. V.57. N04. P.812-819. DOI: 10.1055/a-2495-3296 WOS OpenAlex

Web of science:	WOS:001397271900001
OpenAlex:	W4404957572

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