Novel Methods for Regioselective Vinylic and Aromatic Fluorination

本计画主要研究经由Julia烯化反应来合成乙烯基二醇的新方法。衍生自2-巯基-1，3-苯并噻唑的硫化物将用于在硫化物、亚砜或砜阶段介导氟的α引入。衍生自这些产物的末端α-氟苯并噻唑砜将与醛缩合以产生氟代烯烃。将合成含有区域选择性放置的乙烯基氟的不对称的1，2-二芳基乙烯，然后将其光环化成含有嵌入的菲结构部分的芳基系统。额外的官能团手柄将允许将氟代芳烃精细化为推定的代谢物。将开发的化学也将与闭环复分解反应结合应用，用于合成区域选择性氟化环烯烃。有了这个奖项，有机和大分子化学计划将支持纽约市立大学化学系的Barbara Zajc博士的研究。虽然含有氟原子的有机化合物具有从治疗剂到可用于代谢研究的实体到NMR探针的多种应用，但将氟引入有机分子中仍然代表着一项艰巨的任务。Zajc教授和她的学生正在开发新的方法，用于选择性合成氟化有机化合物及其代谢的推定产物。这种化合物在各种应用中提供了希望，包括分析多环芳烃致癌性的因素。这些研究将由CUNY城市学院的本科生和研究生组成的多元化小组进行。

This project addresses the development of a novel method for vinylic fluorination via the Julia olefination. Sulfides derived from 2-mercapto-1,3-benzothiazole will be used to mediate the alpha introduction of fluorine at the stage of the sulfide, sulfoxide, or sulfone. Terminal alpha-fluorobenzothiazolosulfones derived from these products will be condensed with aldehydes to yield fluoro olefins. Unsymmetrical 1,2-diaryl ethylenes containing a regioselectively placed vinyl fluorine will be synthesized, then photocyclized to aryl systems containing embedded phenanthrenoid moieties. Additional functional group handles will allow for the elaboration of the fluoroaromatics to putative metabolites. The chemistry that will be developed will also be applied in conjunction with ring-closing metathesis reactions for the synthesis of regioselectively fluorinated cyclic olefins.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Barbara Zajc of the Chemistry Department at CUNY City College. While organic compounds containing fluorine atoms have a multitude of applications ranging from therapeutics, to entities useful for metabolic studies to NMR probes, introduction of fluorine into organic molecules continues to represent a formidable task. Professor Zajc and her students are developing new methods for the selective synthesis of fluorinated organic compounds and the putative products of their metabolism. Such compounds offer promise in a variety of applications, including the analysis of the factors responsible for the carcinogenicity of polycyclic aromatic hydrocarbons. These studies will be carried out by a diverse group of undergraduate and graduate students at CUNY City College.