SUGAR AND AMINO ACID SYNTHESIS WITH SPECIFIC LABELING

同位素标记受控手性合成的新方法 糖和氨基酸的提出，基于对糖和氨基酸的有效同源 手性硼酸酯与锂化二氯甲烷反应生成α-氯 在α-碳上具有非常高的非对映选择性的硼酸酯。 初步工作表明，这种同源关系在存在 α-烷氧基和β-烷氧基，因此该过程似乎可以 重复以引入与引入相同数量的相邻氧取代手性中心 想要。两个有用的手性导向基团的对映体， 可供药剂师使用的是蒎烷二醇和2，3-丁二醇 对每个手性中心构型的独立绝对控制。 因为极高的立体选择性和事实是所有的 碳是从二氯甲烷中衍生出来的，这一过程 特别是作为一条通往地区性和地区性的道路 立体标记的糖。几种常见己糖的合成 并提出了戊糖的概念。同时具有~(13)C的甘油醛的制备 以及位于C-3的立体特异的2H标记 概述了1-3H-4-14C-核酮糖-5-磷酸。该方法也会出现 具有特定位置的手性氨基酸制备前景看好 标记，以及手性标记的甲基基团。该计划的最终目的 工作是提供一种简单的方法来获得任何所需的糖、氨基 酸，或具有任何特定组中的任何同位素标记的相关结构 生物化学家想要的位置，以便回答关于 酶反应和代谢途径的机制，这将提供 与各种健康问题相关的基本生化信息。

A new approach to the controlled chiral synthesis isotopically labeled sugars and amino acids is proposed, based on the efficient homologation of chiral boronic esters with lithiated dichloromethane to form Alpha-chloro boronic esters with very high diastereoselection at the Alpha-carbon. Preliminary work has shown that this homologation works in the presence of Alpha- and Beta-alkoxy groups, and it thus appears that the process can be repeated to introduce as many adjacent oxygen-substituted chiral centers as desired. Both enantiomers of the useful chiral directing groups, pinanediol and 2,3-butanediol, are available, giving the chemist independent absolute control of the configuration at each chiral center. Because of the extremely high stereoselectivity and the fact that all of the carbon is derived from dichloromethane, this process appears particularly promising as a route to regiospecifically and stereospecifically labeled sugars. The synthesis of several common hexoses and pentoses is proposed. Preparations of glyceraldehyde having both a 13C and a stereospecific 2H label at C-3 and also of 1-3H-4-14C-ribulose-5-phosphate are outlined. The method also appears highly promising for preparing amino acids with specifically placed chiral labels, and for chirally labeled methyl groups. The ultimate aim of the work is to provide a simple means of obtaining any desired sugar, amino acid, or related structure with any isotopic labels in any set of specific positions that the biochemist wants in order to answer questions about mechanisms of enzyme reactions and metabolic pathways, which will provide basic biochemical information relevant to a wide variety of health problems.