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Oxidative Coupling in Complexity Building Reactions

复杂性构建反应中的氧化偶联

基本信息

批准号：
1764298
负责人：
Marisa Kozlowski
金额：
$ 48.4万
依托单位：
University of Pennsylvania
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-08-01 至 2021-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764298&HistoricalAwards=false
关键词：
Oxidative Coupling Complexity Building Reactions

项目摘要

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Marisa Kozlowski of the Department of Chemistry at the University of Pennsylvania. She is developing new methods to couple molecular fragments into larger molecules. The chemistry allows for these larger molecules to be rapidly assembled in a manner that enables variations in their overall structure. This in turns allows for the study of how those variation alter the molecules properties. The molecules targeted for synthesis have a wide variety of potential applications ranging from their use as semiconductors with charge/energy transport properties for use in organic electronic devices and as liquid crystal materials to pharmaceutical applications in connection with the opium alkaloids. Much of the project lies at the interface of organic, computational, and materials chemistry. Therefore, the diversity of the science being pursued is well suited for the education of scientists at all levels. Broadening the participation of underrepresented populations in chemistry research is a particular focus of Professor Kozlowski with support for the Alliance for Diversity in Science and Engineering (ADSE) at Penn. The principal goals of this research program entail the development of oxidative methods for the coupling of fragments to generate more complex targets. Such routes introduce functionality at non-functionalized centers, thereby eliminating the need for complex pre-functionalized starting materials. The chemistry studied is contributing to environmentally benign methods for chemical synthesis by 1) engineering reactions at non-functionalized centers, thereby eliminating the need for complex pre-functionalized starting materials, 2) using oxygen is used as the terminal oxidizing agent, and 3) using less toxic and less expensive base metals. Transformations that are being pursued include oxidative phenol coupling to bring together three or more aromatic subunits, which are then oxidized further to provide polycyclic aromatic hydrocarbons with selective peripheral functionalization. Kinetic resolution is being explored with oxidative phenol coupling to create complex enantioenriched architectures, such as precursors to the opium alkaloids. Finally, oxidative coupling of the sp3 centers of alkyl arenes with a range of tertiary nucleophiles are being explored. Successful development of the methods is having a broad impact on a number of areas as there is a need to access such structures in the pharmaceutical, chemical, materials science, and agricultural industries as well as in basic biological and chemical research endeavors. The educational plan involves training high school students, undergraduate students, graduate students and postdoctoral researchers as well as outreach to foster inclusion of underrepresented communities into the chemistry research enterprise.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

化学系的化学合成计划支持宾夕法尼亚大学化学系的Marisa Kozlowski教授的项目。她正在研究将分子片段偶联成更大分子的新方法。化学允许这些较大的分子以能够改变其整体结构的方式快速组装。这反过来又允许研究这些变化如何改变分子特性。作为合成目标的分子具有广泛的潜在应用，从它们用作具有电荷/能量传输特性的半导体用于有机电子器件和用作液晶材料到与鸦片生物碱有关的药物应用。这个项目的大部分内容都是有机化学、计算化学和材料化学的结合。因此，所追求的科学的多样性非常适合各级科学家的教育。扩大代表性不足的人群在化学研究中的参与是Kozlowski教授在宾夕法尼亚大学科学与工程多样性联盟（ADSE）的支持下的一个特别重点。该研究计划的主要目标是开发用于片段偶联的氧化方法，以产生更复杂的靶标。此类途径在非官能化中心处引入官能度，从而消除对复杂的预官能化起始材料的需要。所研究的化学有助于通过以下方式实现环境友好的化学合成方法：1）在非官能化中心进行工程化反应，从而消除对复杂的预官能化起始材料的需要; 2）使用氧作为末端氧化剂;以及3）使用毒性较小且较便宜的贱金属。正在进行的转化包括氧化苯酚偶联以将三个或更多个芳族亚基聚集在一起，然后将其进一步氧化以提供具有选择性外围官能化的多环芳烃。动力学拆分正在探索与氧化苯酚偶联，以创建复杂的对映体富集的架构，如鸦片生物碱的前体。最后，正在探索烷基芳烃的sp3中心与一系列叔亲核试剂的氧化偶联。这些方法的成功开发对许多领域产生了广泛的影响，因为在制药、化学、材料科学和农业工业以及基础生物和化学研究工作中都需要使用这种结构。该教育计划包括培训高中生、本科生、研究生和博士后研究人员，以及促进将代表性不足的社区纳入化学研究企业的外展活动。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

期刊论文数量（20）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Enantioselective Vanadium-Catalyzed Oxidative Coupling: Development and Mechanistic Insights.

DOI：
10.1021/acs.joc.8b02083
发表时间：
2018-12-07
期刊：
The Journal of organic chemistry
影响因子：
0
作者：
Kang H;Herling MR;Niederer KA;Lee YE;Vasu Govardhana Reddy P;Dey S;Allen SE;Sung P;Hewitt K;Torruellas C;Kim GJ;Kozlowski MC
通讯作者：
Kozlowski MC

Diastereoselective Synthesis of Benzoxanthenones

苯并杂蒽酮的非对映选择性合成