Novel Methods for Regioselective Vinylic and Aromatic Fluorination

区域选择性乙烯基和芳香族氟化的新方法

• 批准号: 0516557
• 负责人: Barbara Zajc
• 金额: $ 26.6万
• 依托单位: CUNY City College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-09-01 至 2009-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0516557&HistoricalAwards=false
• 关键词: Novel; Methods; Regioselective; Vinylic; Aromatic

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.

该项目致力于开发一种通过 Julia 烯化进行乙烯基氟化的新方法。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。由这些产物衍生的末端α-氟苯并噻唑砜将与醛缩合生成氟代烯烃。将合成含有区域选择性放置的乙烯基氟的不对称 1,2-二芳基乙烯，然后光环化为含有嵌入的菲类部分的芳基系统。额外的官能团处理将允许将含氟芳族化合物精细化为推定的代谢物。将开发的化学方法还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。有机和高分子化学项目获得这一奖项，将支持纽约市立大学城市学院化学系 Barbara Zajc 博士的研究。虽然含有氟原子的有机化合物具有多种应用，从治疗学到可用于代谢研究的实体再到核磁共振探针，但将氟引入有机分子仍然是一项艰巨的任务。 Zajc 教授和她的学生正在开发选择性合成氟化有机化合物及其代谢产物的新方法。此类化合物在多种应用中具有广阔的前景，包括分析多环芳烃致癌性的因素。这些研究将由纽约市立大学城市学院的不同本科生和研究生群体进行。