New Cycloaddition and Annulation Strategies for Organic Synthesis

通过这一奖项，化学系的化学合成计划支持麻省理工学院化学系的Rick L.Danheiser教授的研究。在这项研究计划中，Danheiser教授和他的学生正在开发化学合成环状有机分子的新方法，这些环状有机分子被结合在许多具有生物重要性的化合物的化学结构中。开发高效的合成这些分子的方法对于改善获得在医学、材料化学、农业和电子等领域具有重要应用的化合物具有重要的价值。这项研究计划的目标是开发新的合成策略，使这类化合物的合成过程大大简化。这些新方法在几种天然化合物的合成中的应用证明了这些新方法的有效性，这些化合物具有抗肿瘤活性，但从其自然来源中无法大量获得。这笔助学金资助的研究生担任麻省理工学院外联计划的协调员，该计划每年访问新英格兰地区约25所高中，提供关于化学和科学职业的演讲。每年大约有1,200-1,500名高中生参加这些讲座，其中多达50%的学生是代表不足的少数群体的成员。Danheiser博士也是公认的化学安全领域的领导者。这项研究提高了化学家开发几类重要有机化合物的有效合成的能力，包括多环芳烃分子和杂环系统，如吲哚和吡啶。正在研究的方法涉及机械上的新变换。这些研究进一步加深了对异常反应物种化学的理解，如应变环烯和炔烃、乙烯基烯、乙烯基烯以及其他几类高度不饱和的共轭分子。从可持续性的角度来看，正在开发的方法有几个吸引人的特点。大多数方法是高度原子经济的，即反应物的所有原子都被结合到产品中，最大限度地减少了化学废物的产生。此外，大多数新的环加成反应都是由热或光引发的，从而避免了甚至需要催化量的试剂(特别是重金属催化剂)。合成通常被描述为化学的“使能技术”。这些合成方法为学术界和工业界的研究人员提供了设计和制造杂环化合物的新工具，这些化合物在医学、农业、电子和其他领域都有应用。该计划支持的研究生接受培训，以发展他们作为合成化学家的技能，科学伦理，以及发展他们的口头和书面沟通技能。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With this award, the Chemical Synthesis Program of the Division of Chemistry is supporting the research of Professor Rick L. Danheiser of the Department of Chemistry at the Massachusetts Institute of Technology. In this research program, Professor Danheiser and his students are developing new methods for the chemical synthesis of cyclic organic molecules that are incorporated in the chemical structures of numerous biologically-important compounds. The development of highly efficient methods for the synthesis of these molecules has great value in providing improved access to compounds with important applications in medicine, materials chemistry, agriculture and electronics. The goal of this research program is the development of new synthetic strategies with the power to dramatically streamline the synthesis of these classes of compounds. The utility of these new methods is being demonstrated by their application to the synthesis of several naturally-occurring compounds that have activity as antitumor agents, but which are not available in large quantities from their sources in nature. The graduate students supported under this grant serve as coordinators for the MIT Outreach Program, which each year visits about 25 high schools in the New England region providing presentations on chemistry and careers in science. Approximately 1,200-1,500 high school students attend these presentations each year, with up to 50% of the students being members of underrepresented minority groups. Dr. Danheiser is also a recognized leader in chemical safety.This research advances the ability of chemists to develop efficient syntheses of several important classes of organic compounds including polycyclic aromatic molecules and heterocyclic systems such as indoles and pyridines. The methods under investigation involve mechanistically novel transformations. These studies are furthering the understanding of the chemistry of unusual reactive species such as strained cyclic allenes and alkynes, vinylketenes, vinylallenes, and several other classes of highly unsaturated conjugated molecules. From the perspective of sustainability, the methodology under development has several attractive features. Most of the methods are highly atom economical, i.e., all of the atoms of the reactants are incorporated in the products, minimizing the generation of chemical waste. In addition, most of the new cycloadditions are triggered simply by heat or light, avoiding the need for even catalytic amounts of reagents (especially heavy metal catalysts). Synthesis is often described as the "enabling technology" of chemistry. The synthetic methods provide researchers in both academia and industry with new tools to design and make heterocyclic compounds with applications in medicine, agriculture, electronics, and other areas. The graduate students supported under this program receive training to develop their skills as synthetic chemists, in scientific ethics, and in developing their oral and written communication skills.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.