Uncommon Phosphonylation of Pyrazine‐2,3‐dicarbonitrile Derivatives via C(sp<sup>2</sup>)−CN Bond Cleavage

Volostnykh, M.V.; Enakieva, Y.Y.; Kirakosyan, G.A.; Grigoriev, M.S.; Chufarin, A.E.; Wang, H.; Stuzhin, P.A.; Gorbunova, Y.G.; Tsivadze, A.Y.

Авторы: Volostnykh Marina V., Enakieva Yulia Yu, Kirakosyan Gayane A., Grigoriev Mikhail S., Chufarin Aleksey E., Wang Hailong, Stuzhin Pavel A., Gorbunova Yulia G., Tsivadze Aslan Yu
Журнал: Asian Journal of Organic Chemistry
Том: 14
Номер: 1
Год издания: 2025
Номер статьи: e202400448
DOI: 10.1002/ajoc.202400448
Аннотация: A direct phosphonylation of the C(sp2)−CN bond under mild catalytic and non-catalytic reaction conditions is disclosed. Pyrazine-2,3-dicarbonitriles are readily coupled with HPO(OEt)2 to produce the corresponding dialkoxyphosphoryl-substituted pyrazines. The phosphonylation reaction occurs in the presence of a base (Et3N, Cs2CO3) as nucleophilic substitution of the CN groups. The yield of target diphosphonates depends on the nature of substituents in the 5,6-positions of the pyrazine ring: it exceeds 90 % for di-5,6-aryl-substituted pyrazines and is significantly lower when electron-donating alkyl (n-propyl) groups are attached to the 5,6-positions. It should be noted that for pyrazine-2,3-dicarbonitriles bearing vicinal 4-bromophenyl groups, the nucleophilic phosphonylation leading to C−CN/P−H coupling in the pyrazine ring is predominant over Pd-catalyzed Hirao's C−Br/P−H coupling reaction in phenyl rings. Detailed structural characterization, both in solution by means of 1H, 13C and 31P NMR spectroscopy and in the solid state by single crystal X-ray diffraction, of a series of newly synthesized pyrazine phosphonates is reported.
Добавил в систему: Волостных Марина Владимировна

	ИСТИНА	Войти в систему Регистрация
	ИСТИНА ЦЭМИ РАН
	Главная Поиск Статистика О проекте Помощь

ИСТИНА

ИСТИНА ЦЭМИ РАН

Uncommon Phosphonylation of Pyrazine‐2,3‐dicarbonitrile Derivatives via C(sp<sup>2</sup>)−CN Bond Cleavageстатья

Прикрепленные файлы