VINYL RADICAL-BASED CYCLIZATION OF 6-SUBSTITUTED 1-(2-DEOXY-D-ERYTHRO-PENT-1-ENOFURANOSYL)URACILS - SYNTHESIS OF ANOMERIC SPIRO NUCLEOSIDES

被引：50

作者：

KITTAKA, A ^{[1
]}

TANAKA, H ^{[1
]}

ODANAKA, Y ^{[1
]}

OHNUKI, K ^{[1
]}

YAMAGUCHI, K ^{[1
]}

MIYASAKA, T ^{[1
]}

机构：

[1] SHOWA UNIV,SCH PHARMACEUT SCI,SHINAGAWA KU,TOKYO 142,JAPAN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1994年 / 59卷 / 13期

关键词：

D O I：

10.1021/jo00092a024

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The preparation of 6-bromovinyl derivatives,of 1-(2-deoxy-D-erythro-pent-1-enofuranosyl)uracils (10-13) and their radical-mediated reactions leading to the formation of cyclized products were investigated with the aim of developing a new method for the synthesis of anomeric spiro nucleosides. Treatment of O-2,2'-anhydrouridine 5 with LDA followed by HCO(2)Me gave 1-(2-deoxy-D-erythro-pent-1-enofuranosyl)-6-formyluracil (9). The 6-bromovinyl derivatives 10-13 were prepared by Wittig reaction of 9. Compounds 10, 12, and 13 underwent a vinyl radical-mediated cyclization (Bu(3)SnH/AIBN, in refluxing benzene) preferentially in a 5-exo-trig manner to give 2'-deoxy-6,1'-ethenouridines 14a and 17 and the corresponding a-anomers 15a and 18 with preponderance of the former. The anomeric stereochemistry of these spiro nucleosides was unambiguously determined based on X-ray crystallography and their chemical reactions. Conversion of 14a to 2'-deoxy-6,1'-ethanouridine (26) was also carried out. The present method offers a straightforward synthesis of certain anomeric spiro nucleosides.

引用

页码：3636 / 3641

页数：6

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