Enantioselective Synthesis by Chiral Anion Phase Transfer Catalysis

描述（由申请人提供）：本研究项目的主要目标是基于手性阴离子相转移催化的概念开发催化对映选择性转化，该转化将广泛适用于治疗相关有机分子的制备。为此，提出了几种新的碳-碳键对映选择性反应，重点是sp3-C-F键对映选择性的发展。我们将在阳离子亲电试剂存在的情况下，通过配位磷酸盐衍生的手性阴离子，开发涉及激活pi键作为亲电试剂对杂原子和碳基亲核试剂的反应。我们还将证明这种反应性歧管适用于其他反应类别，如直接对映选择性氟化反应和氟化脱芳化反应。这些方法将被用于氟化构建块、杂环和天然产物类似物的对映选择性构建。因此，我们预计所提出的耐空气和耐湿转化将为合成化学家和生物医学研究人员提供单对映体合成的额外工具。

DESCRIPTION (provided by applicant): The major goal of this research program is to develop catalytic enantioselective transformations based on the concept of chiral anion phase transfer catalysis that will be broadly applicable to the preparation of therapeutically relevant organic molecules. Towards this end, several new enantioselective reactions of carbon-carbon pi-bonds are proposed, with a major emphasis placed on the development of enantioselective sp3-C-F bond construction. We will develop reactions that involve activation of pi-bonds as electrophiles towards heteroatom and carbon-based nucleophiles, by coordination phosphate-derived chiral anions in the presence of cationic electrophiles. We will also demonstrate that this reactivity manifold is applicable to other reaction classes, such as direct enantioselective fluorination reactions and fluorinated dearomatization. These methods will be exploited in the enantioselective construction of fluorinated building blocks, heterocycles and natural product analogs. Thus, we anticipate that the proposed air and moisture tolerant transformations will provide synthetic chemists and biomedical researchers with additional tools for single enantiomer synthesis.