Unexpected Observation of the Dimroth Rearrangement in the Ribosylation of 4‑Aminopyrimidines

A method for the preparation of 1-(N-ribofuranosyl)-6-imino-1,6-dihydropyrimidin-4-amines 3 or 4-(N-ribofuranosyl)-6-aminopyrimidines 4 via glycosylation of 4-aminopyrimidines 2 or 5 is described. Silylated 4-aminopyrimidines 2 or 5 upon ribosylation with 1 provide products 3. When intermediates 3 c...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 82; no. 11; pp. 5881 - 5889
Main Authors Baiazitov, Ramil Y, Sydorenko, Nadiya, Ren, Hongyu, Moon, Young-Choon
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 02.06.2017
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
SERIES
MUSHROOM CLITOCYBE-INVERSA
ANALOGS
DIGLYCOSYLAMINES
BIOLOGICAL EVALUATION
AMINO NUCLEOSIDE
INSECTICIDAL NUCLEOSIDE
GLYCOSYLAMINES
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Summary:A method for the preparation of 1-(N-ribofuranosyl)-6-imino-1,6-dihydropyrimidin-4-amines 3 or 4-(N-ribofuranosyl)-6-aminopyrimidines 4 via glycosylation of 4-aminopyrimidines 2 or 5 is described. Silylated 4-aminopyrimidines 2 or 5 upon ribosylation with 1 provide products 3. When intermediates 3 contain a strongly electron-withdrawing group, such as C(4)-Cl or C(5)-NO2, they rearrange to products 4 in the presence of aqueous ammonia. A mechanism is proposed that involves a ring-opening/ring-closing (Dimroth) rearrangement.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.7b00780