Molecular design of a new class of spin-labeled ribonucleosides with N-tert-butylaminoxyl radicals

Mariko Aso, T. Ikeno, K. Norihisa, M. Tanaka, N. Koga, H. Suemune

研究成果: ジャーナルへの寄稿記事

18 引用 (Scopus)

抄録

We designed a new type of spin-labeled nucleosides with an N-tert-butylaminoxyl radical which is introduced to the nucleobase directly. Purine and pyrimidine ribonucleosides containing the aminoxyl radical such as 1a-d, 2, 3, and 4 were synthesized to investigate the stability and behavior of the N-tert-butylaminoxyl radical on a nucleobase. Lithiation of tri-O-silylated 6-chloropurine ribonucleoside (5) followed by reaction with 2-methyl-2-nitrosopropane (MNP) gave the key compound 6a, which was further converted to 6b-d. Oxidation of the obtained 6a-d and their triols (7a-d) with Ag2O led to formation of the corresponding stable spin-labeled nucleosides (8a-d and 1a-d), which were confirmed by EPR spectroscopy. Similarly, the precursors of spin-labeled pyrimidines (13, 20, and 23) were synthesized by site-selective lithiation of tri-O-protected pyrimidine derivatives (9, 18, and 21) followed by the reaction with MNP and deprotection. An EPR study showed that the aminoxyl radicals (2, 3, and 4) were stable and that their hyperfine structures were dependent on the position of the radical. Electron densities of pyrimidine also affected hyperfine structures.

元の言語英語
ページ(範囲)3513-3520
ページ数8
ジャーナルJournal of Organic Chemistry
66
発行部数10
DOI
出版物ステータス出版済み - 5 18 2001

Fingerprint

Ribonucleosides
Nucleosides
Paramagnetic resonance
Pyrimidines
Carrier concentration
Spectroscopy
Derivatives
Oxidation
pyrimidine

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

これを引用

Molecular design of a new class of spin-labeled ribonucleosides with N-tert-butylaminoxyl radicals. / Aso, Mariko; Ikeno, T.; Norihisa, K.; Tanaka, M.; Koga, N.; Suemune, H.

:: Journal of Organic Chemistry, 巻 66, 番号 10, 18.05.2001, p. 3513-3520.

研究成果: ジャーナルへの寄稿記事

Aso, Mariko ; Ikeno, T. ; Norihisa, K. ; Tanaka, M. ; Koga, N. ; Suemune, H. / Molecular design of a new class of spin-labeled ribonucleosides with N-tert-butylaminoxyl radicals. :: Journal of Organic Chemistry. 2001 ; 巻 66, 番号 10. pp. 3513-3520.
@article{3071455500c948a09e7c93a567e777de,
title = "Molecular design of a new class of spin-labeled ribonucleosides with N-tert-butylaminoxyl radicals",
abstract = "We designed a new type of spin-labeled nucleosides with an N-tert-butylaminoxyl radical which is introduced to the nucleobase directly. Purine and pyrimidine ribonucleosides containing the aminoxyl radical such as 1a-d, 2, 3, and 4 were synthesized to investigate the stability and behavior of the N-tert-butylaminoxyl radical on a nucleobase. Lithiation of tri-O-silylated 6-chloropurine ribonucleoside (5) followed by reaction with 2-methyl-2-nitrosopropane (MNP) gave the key compound 6a, which was further converted to 6b-d. Oxidation of the obtained 6a-d and their triols (7a-d) with Ag2O led to formation of the corresponding stable spin-labeled nucleosides (8a-d and 1a-d), which were confirmed by EPR spectroscopy. Similarly, the precursors of spin-labeled pyrimidines (13, 20, and 23) were synthesized by site-selective lithiation of tri-O-protected pyrimidine derivatives (9, 18, and 21) followed by the reaction with MNP and deprotection. An EPR study showed that the aminoxyl radicals (2, 3, and 4) were stable and that their hyperfine structures were dependent on the position of the radical. Electron densities of pyrimidine also affected hyperfine structures.",
author = "Mariko Aso and T. Ikeno and K. Norihisa and M. Tanaka and N. Koga and H. Suemune",
year = "2001",
month = "5",
day = "18",
doi = "10.1021/jo015532s",
language = "English",
volume = "66",
pages = "3513--3520",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Molecular design of a new class of spin-labeled ribonucleosides with N-tert-butylaminoxyl radicals

AU - Aso, Mariko

AU - Ikeno, T.

AU - Norihisa, K.

AU - Tanaka, M.

AU - Koga, N.

AU - Suemune, H.

PY - 2001/5/18

Y1 - 2001/5/18

N2 - We designed a new type of spin-labeled nucleosides with an N-tert-butylaminoxyl radical which is introduced to the nucleobase directly. Purine and pyrimidine ribonucleosides containing the aminoxyl radical such as 1a-d, 2, 3, and 4 were synthesized to investigate the stability and behavior of the N-tert-butylaminoxyl radical on a nucleobase. Lithiation of tri-O-silylated 6-chloropurine ribonucleoside (5) followed by reaction with 2-methyl-2-nitrosopropane (MNP) gave the key compound 6a, which was further converted to 6b-d. Oxidation of the obtained 6a-d and their triols (7a-d) with Ag2O led to formation of the corresponding stable spin-labeled nucleosides (8a-d and 1a-d), which were confirmed by EPR spectroscopy. Similarly, the precursors of spin-labeled pyrimidines (13, 20, and 23) were synthesized by site-selective lithiation of tri-O-protected pyrimidine derivatives (9, 18, and 21) followed by the reaction with MNP and deprotection. An EPR study showed that the aminoxyl radicals (2, 3, and 4) were stable and that their hyperfine structures were dependent on the position of the radical. Electron densities of pyrimidine also affected hyperfine structures.

AB - We designed a new type of spin-labeled nucleosides with an N-tert-butylaminoxyl radical which is introduced to the nucleobase directly. Purine and pyrimidine ribonucleosides containing the aminoxyl radical such as 1a-d, 2, 3, and 4 were synthesized to investigate the stability and behavior of the N-tert-butylaminoxyl radical on a nucleobase. Lithiation of tri-O-silylated 6-chloropurine ribonucleoside (5) followed by reaction with 2-methyl-2-nitrosopropane (MNP) gave the key compound 6a, which was further converted to 6b-d. Oxidation of the obtained 6a-d and their triols (7a-d) with Ag2O led to formation of the corresponding stable spin-labeled nucleosides (8a-d and 1a-d), which were confirmed by EPR spectroscopy. Similarly, the precursors of spin-labeled pyrimidines (13, 20, and 23) were synthesized by site-selective lithiation of tri-O-protected pyrimidine derivatives (9, 18, and 21) followed by the reaction with MNP and deprotection. An EPR study showed that the aminoxyl radicals (2, 3, and 4) were stable and that their hyperfine structures were dependent on the position of the radical. Electron densities of pyrimidine also affected hyperfine structures.

UR - http://www.scopus.com/inward/record.url?scp=0035906510&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035906510&partnerID=8YFLogxK

U2 - 10.1021/jo015532s

DO - 10.1021/jo015532s

M3 - Article

VL - 66

SP - 3513

EP - 3520

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 10

ER -