Unexpected one-pot formation of the 1H-6a,8a-epiminotri-cyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study

Unexpected one-pot formation of the 1H-6a,8a-epiminotri-cyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study Full article

Journal

Beilstein Journal of Organic Chemistry
ISSN: 1860-5397

Output data

Year: 2019, Volume: 15, Pages: 2664-2670 Pages count : 7 DOI: 10.3762/bjoc.15.259

Tags

domino reactions; EPR; nitroxide; spin relaxation

Authors

Dobrynin Sergey A. ^1,2 , Kirilyuk Igor A. ^1,2 , Gatilov Yuri, V ¹ , Kuzhelev Andrey A. ^1,2 , Krumkacheva Olesya A. ^2,3 , Fedin Matvey, V ^2,3 , Bowman Michael K. ^1,4 , Bagryanskaya Elena G. ^1,2

Affiliations

1	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Lavrentiev Ave 9, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Pirogova Str 2, Novosibirsk 630090, Russia
3	(Данные Web of science) Int Tomog Ctr SB RAS, Inst Skaya Str 3a, Novosibirsk 630090, Russia
4	(Данные Web of science) Univ Alabama, Tuscaloosa, AL 35487 USA

The unexpected formation of a highly strained polycyclic amine was observed in a one-pot synthesis from cyclopentanone, dimethyl fumarate and ammonium acetate. This multistep reaction includes 1,3-dipolar cycloaddition of dimethyl fumarate to the cyclic azomethine glide formed in situ from cyclopentanone and ammonia. The polycyclic amine product was easily converted into a sterically shielded polycyclic nitroxide. The EPR spectra and spin relaxation behavior of the nitroxide were studied in solution. The spin relaxation seems well suited for the use as a biological spin label and are comparable with those of cyclic nitroxides with two spirocyclic moieties adjacent to the N-O-center dot group.

Dobrynin S.A. , Kirilyuk I.A. , Gatilov Y.V. , Kuzhelev A.A. , Krumkacheva O.A. , Fedin M.V. , Bowman M.K. , Bagryanskaya E.G.
Unexpected one-pot formation of the 1H-6a,8a-epiminotri-cyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study

Beilstein Journal of Organic Chemistry. 2019. V.15. P.2664-2670. DOI: 10.3762/bjoc.15.259 WOS Scopus РИНЦ

Full text from publisher

Published online:

Nov 7, 2019

Web of science	WOS:000494952000001
Scopus	2-s2.0-85076027656
Elibrary	43213891
OpenAlex	W2969228173