SYNTHESIS OF A-HYDROXYCARBONYL COMPOUNDS

拟议工作的目的是为直接 烯醇酸盐的氧化和不对称氧化合成α-羟基羰基 化合物(R2C(OH)C(O)-Z)。具有α-羟基羰基的化合物 结构单元在本质上无处不在，并负责 许多具有这个亚基的化合物的生物活性。这些目标 将通过探索烯醇酸盐(烯醇硅醚， 烯胺、金属烯胺)使用2-磺酰氧氮杂氮杂环丙烷，无质子性和中性 氧化剂。使用这些试剂的手性烯烃的氧化是 预计将在 高光学纯度。手性2-磺酰基-2-烯醇酯氧化反应的研究 和2-磺胺基咪唑氮杂环丙烷将提供对 不对称诱导与电泳烯醇化的新信息 轨迹。金属辅助的不对称氧化反应 具有金属螯合官能团的2-磺胺基咪唑并氮杂环丙烷是 有望得到高对映体的α-羟基羰基化合物 纯洁。该方法学将应用于手性合成。 (-)-丁香酚和(+)-去甲氧基柔红霉素；后者是一种有效的 抗肿瘤药物。 烯醇直接氧化和不对称烯醇氧化作为一种新型催化剂的可行性 合成α-羟基羰基化合物的可行路线是 初步研究证明。

The aim of the proposed work is to develop methodology for the direct oxidation and asymmetric oxidation of enolates to Alpha-hydroxycarbonyl compounds (R2C(OH)C(O)-Z). Compounds having the Alpha-hydroxycarbonyl structural unit are ubiquitous in nature and responsible, for the biological activity of many compounds having this subunit. These goals will be achieved by exploring the oxidation of enolates (enol silyl ethers, enamines, metaloenamines) using 2-sulfonyloxaziridines, aprotic and neutral oxidizing agents. Oxidation of chiral enolates using these reagents is anticipated to give optically active Alpha-hydroxycarbonyl compounds in high optical purity. Studies of enolate oxidations with chiral 2-sulfonyl- and 2-sulfamyloxaziridines will provide insights into the origins of asymmetric induction and new information on electrophile-enolate trajectories. Metal assisted asymmetric oxidations using 2-sulfamyloxaziridines having metal chelating functional groups are anticipated to give Alpha-hydroxycarbonyl compounds in high enantiotopic purity. This methodology will be applied to the chiral synthesis of (-)-Eucomol and (+)-demethoxydaunomycinone; the latter compound is a potent anti-tumor agent. The feasibility of direct enolate and asymmetric enolate oxidation as a viable synthetic route to Alpha-hydroxycarbonyl compounds has been demonstrated by preliminary studies.