Asymmetric Synthesis of Complex Molecules Using Polyfunctional Cyclopropanes

在这个由化学系化学合成计划资助的项目中，安德鲁·哈内德教授正在开发新的合成方法，该方法基于一系列独特的小分子所表现出的不同寻常的反应性。除了探索这些小分子环丙烷的反应性外，正在开发新的催化剂来将这些材料合成为单一立体异构体。使用这种方法正在合成几种具有生物活性的天然产物。除了这些实验室工作外，从这项工作中挑选出来的数据正被用来填充一个基于网络的核磁共振FID数据库，该数据库也在PI的实验室开发中。这一独特的教育资源正在向世界各地的教师提供。该项目的化学重点是开发有效合成复杂分子的新方法。主要目标是利用高度官能化的三环环丙烷家族固有的不寻常的反应模式。将这些化合物与亲核剂或亲电剂反应，可得到具有高区域和立体选择性的高官能化、开环产物。在新型手性芳基碘催化剂的作用下，合成了合成环丙烷所必需的对苯二酚对映体。在这些方法学研究的同时，独特的环丙烷正被用作几种天然产品的关键中间体，特别是氮杂菲内酯和布里烷二萜类化合物。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Andrew Harned is developing new synthetic methodologies based on the unusual reactivity displayed by a family of unique small molecules. In addition to exploring the reactivity of these small-molecule cyclopropanes, new catalysts are being developed to synthesize these materials as single stereoisomers. Several biologically active natural products are being synthesized using this methodology. In addition to these laboratory efforts, selected data from this work are being used to populate a web-based NMR FID database that is also under development in the PI's laboratory. This unique educational resource is being made available to instructors around the world.The chemical focus of the project concerns the development of new methodology for the efficient synthesis of complex molecules. The main goal is to harness the unusual reactivity patterns inherent to a family of highly functionalized, tricyclic cyclopropanes. Reacting these compounds with either nucleophiles or electrophiles affords highly functionalized, ring-opened products with high regio- and stereoselectivity. The requisite starting materials for the cyclopropanes, enantioenriched para-quinols, are synthesized with new chiral aryl iodide catalysts. Concurrent with these methodology studies, the unique cyclopropanes are being used as key intermediates for the construction of several natural products, specifically azaphilone lactones and briarane diterpenoids.