Chiral Vinyloxiranes as Synthetic Intermediates

有机合成计划正在资助詹姆斯·a·马歇尔博士继续进行的研究。马歇尔博士将继续开发新的方法来控制复杂系统合成中的立体化学。这些将为我们的农业和工业所需要的日益复杂的化合物提供所需的新工具。该研究将探索非外消旋乙烯基氧烷作为合成各种聚丙酸酯和相关天然产物亚基的关键中间体的反应范围。这些实验旨在揭示内在的立体偏好，并探索在这些反应中导向基团的作用。各种亲核试剂将被测试，包括非消旋铜酸盐和烯丙基金属化合物。通过适当选择双键几何结构、环氧化物立体化学和试剂立体化学，应该可以对多个立体中心的形成进行相当大的控制。我们还将探讨将上述反应的产物转化为具有潜在抗肿瘤、抗生素和免疫抑制特性的天然产物和类似物的方法。

The Organic Synthesis Program is funding a continuation of the research of Dr. James A. Marshall. Dr. Marshall will continue his development of new ways to control the stereochemistry in the synthesis of complex systems. These will provide the new tools required by the increasing complexity of the compounds needed by our agriculture and industry. The research will explore the scope of reactions in which nonracemic vinyloxiranes serve as key intermediates for the synthesis of subunits found in various polypropionate and related natural products. The experiments are designed to reveal intrinsic steric preferences and explore the role of directing groups in these reactions. A variety of nucleophilic reagents will be tested including nonracemic cuprates and allylmetallic compounds. By the proper selection of double bond geometry, epoxide stereochemistry and reagent sterochemistry it should be possible to exercise considerable control over the formation of multiple stereocenters. Methodology will also be explored for transforming the products of the foregoing reactions into natural products and analogs with potential antitumor, antibiotic, and immunosuppressive properties.