Synlett 2009(4): 599-602  
DOI: 10.1055/s-0028-1087920
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Oxidation of Biginelli Reaction Products: Synthesis of 2-Unsubstituted 1,4-Dihydropyrimidines, Pyrimidines, and 2-Hydroxypyrimidines

Sam Sik Kima, Bo Seung Choia, Jae Hoon Leea, Ki Kon Leea, Tae Hee Leea, Young Ho Kimb, Hyunik Shin*a
a Chemical Development Division, LG Life Sciences, Ltd./R&D, 104-1, Moonji-dong, Yusong-gu, Daejon 305-380, Korea
Fax: +82(42)8665754; e-Mail: hisin@lgls.com;
b Department of Fine Chemical Engineering & Applied Chemistry, BK21-E2M, Chungnam National University, Daejeon 305-764, Korea
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Publication History

Received 28 October 2008
Publication Date:
16 February 2009 (online)

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Abstract

We have devised a new route toward 2-unsubstituted pyrimidine derivatives from the Biginelli product, dihydropyrimidin-2(1H)-thiones in two steps: Oxidation of dihydropyrimidin-2(1H)-thiones using oxone on wet alumina or hydrogen peroxide in the presence of catalytic amount of vanadyl sulfate provided 1,4-di­hydropyrimidine, which was further oxidized to 2-unsubstituted ­pyrimidines by the treatment of KMnO4. Oxidation of dihydropyrimidin-2(1H)-ones by KMnO4 formed 2-hydroxypyrimidine in excellent yield, whereas attempted direct desulfurative aromatization of dihydropyrimidin-2(1H)-thiones by KMnO4 resulted in the formation of 2-hydroxypyrimidines, the same products obtained in the oxidation of dihydropyrimidin-2(1H)-one.