Stereocontrolled photocyclization of 1,2-diketones:: Application of a 1,3-acetyl group transfer methodology to carbohydrates
Stereocontrolled photocyclization of 1,2-diketones:: Application of a 1,3-acetyl group transfer methodology to carbohydrates
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DOI：
10.1021/jo702663w
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发表时间：
2008-05-02
影响因子：
3.6
通讯作者：
Suarez, Ernesto
中科院分区：
文献类型：
--
作者：
Herrera, Antonio J.;Rondon, Maria;Suarez, Ernesto
使用可见光光解 1-糖基-2,3-丁二酮衍生物是合成手性 1-羟基-1-甲基-5-氧杂螺[3.5]壬南-2-酮碳水化合物衍生物的温和且选择性的程序。结果强烈表明环化的立体控制依赖于构象和立体电子因素。 1-羟基-1-甲基-2-环丁酮部分的进一步氧化打开提供了C-和O-糖苷系列中的新C-酮苷衍生物。这种串联的两步过程可以被认为是乙酰基的立体控制 1,3-转移，并且可以应用于吡喃糖和呋喃糖模型。
Photolysis of 1-glycosyl-2,3-butanodione derivatives using visible light is a mild and selective procedure for the synthesis of chiral 1-hydroxy-1-methyl-5-oxaspiro[3.5]nonan-2-one carbohydrate derivatives. The results strongly suggest that stereocontrol of the cyclization is dependent on conformational and stereoelectronic factors. Further oxidative opening, of the 1-hydroxy-1-methyl-2-cyclobutanone moiety affords new C-ketoside derivatives either in C- and O-glycoside series. This tandem two-step process could be considered to be a stereocontrolled 1,3-transference of an acetyl group, and it can be applied either to pyranose and furanose models.