Asymmetric Synthesis with Boronic Esters

有机合成计划提供支持，以继续唐纳德·S·马特森教授在华盛顿州立大学化学系用硼酸酯进行的不对称合成研究。Matteson教授将研究不对称硼酸酯的环化反应以获得手性环丁烷，为合成以棉铃象甲酚为代表的天然产物提供了一条新的路线。将开发可将硼酸酯转化为烷基二卤代硼烷的反应，这些反应将通过亲核中心的分子内传递进行修饰，以提供含氮和含氧杂环的新合成。将分析碳-碳键形成中的催化手性控制，以及导致碳-硼键转化为碳-氮和碳-碳键的反应。这些研究将为C2-手性二胺的制备和反消旋反应的研究打开大门，使外消旋的硼酸酯底物完全转化为单一的非对映异构体产物。存在着许多分子，它们与镜像的关系就像右手熊与左手的关系一样--它们看起来一样，但并不完全相同。通常，一种形式的分子会表现出与其镜像形式不同的性质，特别是在生物活性方面，因此合成有机化学家必须设计出制备所需分子的单一形式的方法。马特森教授将通过发展含硼化合物的化学，利用此类化合物不同寻常的化学反应能力，促进新的碳-碳和碳-氮键的形成，来探索这种“不对称”合成。他将开发通向各种化合物的路线，提供建立不对称合成领域的一般基础，并将通过合成一种可能用作棉铃象甲虫侵害剂的分子来强调化学的实用价值。

Support is provided by the Organic Synthesis Program to continue Professor Donald S. Matteson's studies of asymmetric synthesis with boronic esters in the Department of Chemistry at Washington State University. Professor Matteson will examine the cyclization of asymmetric boronic esters to obtain chiral cyclobutanes, providing a new route for the synthesis of natural products, typified by the boll weevil pheremone, grandisol. Reactions allowing the conversion of boronic esters to alkyldihaloboranes will be developed, and these reactions will be modified through intramolecular delivery of nucleophilic centers to afford new syntheses of nitrogen- and oxygen-containing heterocycles. Catalytic chirality control in the formation of carbon-carbon bonds will be assayed, as will reactions resulting in the conversion of carbon-boron bonds to carbon-nitrogen and carbon-carbon bonds. These studies will open the doors for the preparation of C2-chiral diamines and the study of retroracemization reactions, allowing complete conversion of racemic boronic ester substrates to a single diastereomeric product. Many molecules exist which bear the same relationship to their mirror image as a right hand bears to a left hand - they look the same, but they are not identical. Often, one form of a molecule will display different properties, particularly with regards to biological activity, than those of its mirror image form, and thus synthetic organic chemists must devise methods for the preparation of single forms of desired molecules. Professor Matteson will explore such `asymmetric` syntheses by developing the chemistry of compounds containing boron, exploiting the unusual chemical reactivity of such compounds to facilitate the formation of new carbon-carbon and carbon-nitrogen bonds. He will develop routes to broad classes of compounds, providing a general foundation on which to build the field of asymmetric synthesis, and also will highlight the practical utility of the chemistry through the synthesis of a molecule which may serve as an agent for the control of boll weevil infestations.