Enantioselective Synthesis by Chiral Anion Phase Transfer Catalysis

描述(申请人提供)：本研究计划的主要目标是开发基于手性阴离子相转移催化概念的催化对映体选择性转化，这将广泛适用于制备具有治疗意义的有机分子。为此，提出了几种新的碳-碳pi键的对映选择性反应，重点介绍了对映选择性SP3-C-F键结构的研究进展。我们将通过在阳离子亲电体存在的情况下配位磷酸盐衍生的手性阴离子来开发涉及作为亲电体的pi-键对杂原子和碳基亲核体的活化的反应。我们还将证明这种反应性流形也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构化反应。这些方法将被用于含氟构筑块、杂环和天然产物类似物的对映选择性构建。因此，我们预计，拟议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合成单一对映体的额外工具。

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.