Synthesis of 1-Deoxy-D-xylulose and 1-Deoxy-D-xylulose-5-phosphate.
Synthesis of 1-Deoxy-D-xylulose and 1-Deoxy-D-xylulose-5-phosphate.
复制标题
1-脱氧-D-木酮糖和1-脱氧-D-木酮糖-5-磷酸的合成。
DOI：
10.1021/jo981966k
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发表时间：
1999
期刊：
影响因子：
--
通讯作者：
Poulter,C.Dale
中科院分区：
文献类型：
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作者：
Blagg,BrianS.J.;Poulter,C.Dale
1-脱氧-d-木酮糖（4）和相应的5-磷酸（5）是生物合成二磷酸硫胺素（维生素B1）、磷酸吡哆醇（维生素B6）和最近在细菌和植物叶绿体中发现的非甲羟戊酸类异戊二烯化合物家族中第一途径特异性酶的底物。4和5均由市售的（−）-2，3-O-异亚丙基-d-苏糖醇（10）合成。在四个步骤中将保护的四醇转化为（−）-3，4-O-异亚丙基-5-三异丙基甲硅烷基-1-脱氧-木酮糖（14）。用乙酸处理14得到4，总收率为69%。通过保护14中的羰基，除去三异丙基甲硅烷基部分，并将所得醇用亚磷酸三甲酯/TeCl 4、三甲基溴化甲硅烷基、水和HCl连续处理，得到相应的5-磷酸酯，以58%的总收率从10得到5。
1-Deoxy-d-xylulose (4) and the corresponding 5-phosphate (5) are substrates for the first pathway-specific enzymes in the biosynthesis of thiamine diphosphate (vitamin B1), pyridoxol phosphate (vitamin B6), and the nonmevalonate family of isoprenoid compounds recently discovered in bacteria and plant chloroplasts. Both4and5were synthesized from commercially available (−)-2,3-O-isopropylidene-d-threitol (10). The protected tetraol was converted to (−)-3,4-O-isopropylidene-5-triisopropylsilyl-1-deoxy-d-xylulose (14) in four steps. Treatment of14with acetic acid gave4in an overall yield of 69%. The corresponding 5-phosphate was obtained by protection the carbonyl group in14, removal of the triisopropylsilyl moiety, and treatment of the resulting alcohol with trimethyl phosphite/TeCl4, trimethylsilyl bromide, water, and HCl in successive steps to give5in 58% overall yield from10.