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

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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. / Dobrynin, Sergey A.; Kirilyuk, Igor A.; Gatilov, Yuri V. et al.

In: Beilstein Journal of Organic Chemistry, Vol. 15, 07.11.2019, p. 2664-2670.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{2f3dd31f9e6a41eeba41eeedfc08d7ac,

title = "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",

abstract = "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 ylide 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· group.",

keywords = "Domino reactions, EPR, Nitroxide, Spin relaxation, DISTANCE MEASUREMENTS, RELAXATION RATES, PROTEIN, domino reactions, spin relaxation, nitroxide, RADICALS, SPIN-LABEL",

author = "Dobrynin, {Sergey A.} and Kirilyuk, {Igor A.} and Gatilov, {Yuri V.} and Kuzhelev, {Andrey A.} and Krumkacheva, {Olesya A.} and Fedin, {Matvey V.} and Bowman, {Michael K.} and Bagryanskaya, {Elena G.}",

note = "Copyright {\textcopyright} 2019, Dobrynin et al.; licensee Beilstein-Institut.",

year = "2019",

month = nov,

day = "7",

doi = "10.3762/bjoc.15.259",

language = "English",

volume = "15",

pages = "2664--2670",

journal = "Beilstein Journal of Organic Chemistry",

issn = "1860-5397",

publisher = "Beilstein-Institut Zur Forderung der Chemischen Wissenschaften",

}

RIS

TY - JOUR

T1 - 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

AU - Dobrynin, Sergey A.

AU - Kirilyuk, Igor A.

AU - Gatilov, Yuri V.

AU - Kuzhelev, Andrey A.

AU - Krumkacheva, Olesya A.

AU - Fedin, Matvey V.

AU - Bowman, Michael K.

AU - Bagryanskaya, Elena G.

PY - 2019/11/7

Y1 - 2019/11/7

N2 - 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 ylide 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· group.

AB - 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 ylide 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· group.

KW - Domino reactions

KW - EPR

KW - Nitroxide

KW - Spin relaxation

KW - DISTANCE MEASUREMENTS

KW - RELAXATION RATES

KW - PROTEIN

KW - domino reactions

KW - spin relaxation

KW - nitroxide

KW - RADICALS

KW - SPIN-LABEL

UR - http://www.scopus.com/inward/record.url?scp=85076027656&partnerID=8YFLogxK

U2 - 10.3762/bjoc.15.259

DO - 10.3762/bjoc.15.259

M3 - Article

C2 - 31807201

AN - SCOPUS:85076027656

VL - 15

SP - 2664

EP - 2670

JO - Beilstein Journal of Organic Chemistry

JF - Beilstein Journal of Organic Chemistry

SN - 1860-5397

ER -

ID: 22576467