Research output: Contribution to journal › Article › peer-review
DBU-Promoted Cyclizations of Cyclopentyl-Substituted Oxazapolyenes to Cyclopentapyridones and Hydroxypyrroles: Experimental and DFT Study. / Филиппов, Илья Павлович; Захаров, Тимофей Николаевич; Гришин, Александр Валерьевич; Хлебников, Александр Феодосиевич; Новиков, Михаил Сергеевич; Ростовский, Николай Витальевич.
In: The Journal of organic chemistry, Vol. 89, No. 21, 04.10.2024, p. 15404–15413.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - DBU-Promoted Cyclizations of Cyclopentyl-Substituted Oxazapolyenes to Cyclopentapyridones and Hydroxypyrroles: Experimental and DFT Study
AU - Филиппов, Илья Павлович
AU - Захаров, Тимофей Николаевич
AU - Гришин, Александр Валерьевич
AU - Хлебников, Александр Феодосиевич
AU - Новиков, Михаил Сергеевич
AU - Ростовский, Николай Витальевич
PY - 2024/10/4
Y1 - 2024/10/4
N2 - 1,1-Di(alkoxycarbonyl)-4-cyclopentyl-2-azabuta-1,3-dienes react with DBU to form two types of heterocyclic products: 1H-cyclopenta[c]pyrid-1-ones and 3-hydroxy-1H-pyrroles. These previously unobserved transformations proceed through the formation of 1-azapentadienyl anion which undergoes 1,6-shift of the alkoxycarbonyl group to the cyclopentyl moiety followed by 1,6-cyclization to form the cyclopentapyridone (path a) and 1,5-cyclization accompanied by 1,3-shift of the methoxy group followed by dialkyl carbonate elimination to afford the hydroxypyrrole (path b). The mechanisms of the reactions were studied using DFT calculations. Pyridones can be synthesized in one pot in three steps via Rh(II)-catalyzed isomerization of 4-cyclopentylisoxazoles to 2H-azirines and their subsequent reaction with diazomalonic esters, followed by heating of the resulting 2-azabuta-1,3-dienes with DBU.
AB - 1,1-Di(alkoxycarbonyl)-4-cyclopentyl-2-azabuta-1,3-dienes react with DBU to form two types of heterocyclic products: 1H-cyclopenta[c]pyrid-1-ones and 3-hydroxy-1H-pyrroles. These previously unobserved transformations proceed through the formation of 1-azapentadienyl anion which undergoes 1,6-shift of the alkoxycarbonyl group to the cyclopentyl moiety followed by 1,6-cyclization to form the cyclopentapyridone (path a) and 1,5-cyclization accompanied by 1,3-shift of the methoxy group followed by dialkyl carbonate elimination to afford the hydroxypyrrole (path b). The mechanisms of the reactions were studied using DFT calculations. Pyridones can be synthesized in one pot in three steps via Rh(II)-catalyzed isomerization of 4-cyclopentylisoxazoles to 2H-azirines and their subsequent reaction with diazomalonic esters, followed by heating of the resulting 2-azabuta-1,3-dienes with DBU.
U2 - 10.1021/acs.joc.4c00647
DO - 10.1021/acs.joc.4c00647
M3 - Article
VL - 89
SP - 15404
EP - 15413
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 21
ER -
ID: 126734172