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Development of Catalytic Enantioselective Intermolecular Diene Hydrofunctionalization Reactions

催化对映选择性分子间二烯氢官能化反应的进展

基本信息

批准号：
1800012
负责人：
Steven Malcolmson
金额：
$ 42万
依托单位：
Duke University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-07-15 至 2022-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800012&HistoricalAwards=false
关键词：
Development Catalytic Enantioselective Intermolecular Diene

项目摘要

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Steven Malcolmson. Professor Malcolmson is a faculty member in the Department of Chemistry at Duke University. The development of new chemical reactions is critical to continued progress within a number of vital technologies, including materials, agriculture, and pharmaceuticals. The needs for the development of synthetic methods include the use of cheap and abundant starting materials while generating minimal chemical waste. One reaction of interest, called a catalytic hydrofunctionalization, adds new abilities to change to readily available molecules. Hydrofunctionalization reactions are currently limited in terms of the types of molecules that can be used and the speed and selectivity of the overall process. To address these limitations, the Malcolmson laboratory is developing a number of new hydrofunctionalization reactions that form carbon-carbon and carbon-nitrogen bonds. The reactions take advantage of commercially available reagents and easily accessed starting materials, and they incorporate all of the atoms from all reagents into the products (atom economy) while using minimal solvent. As such, the reactions generate very little chemical waste. The products generated from the reactions are valuable in that they can serve as synthetic building blocks for use in the fine chemical, agrochemistry, and medicinal chemistry industries. In addition to this work, Dr. Malcolmson and his team are developing a series of short online videos to educate the public and undergraduate and graduate students about how the development of catalytic reactions has shaped the modern world through industrial applications. This effort increases public scientific literacy and fosters an interest in science among precollege and college students while also broadening graduate education, thereby helping to train the next generation of scientists.With funding from the Chemical Synthesis Program of the Chemistry Division, the Malcolmson laboratory at Duke University is developing a number of catalytic site- and enantioselective hydroamination and hydroalkylation reactions of acyclic 1,3-dienes, including challenging internal dienes. Palladium-based catalysts with chiral chelating P,N-ligands allow for efficient and enantioselective reactions of cheap, abundant, and commercially available amines and beta-dicarbonyl pronucleophiles at room temperature within short reaction times. Hydrofunctionalization of dienes offers an expedient and 100% atom economical way to construct compounds with allylic stereogenic centers, valuable building blocks for assembling fine chemicals, agrochemicals, and pharmaceuticals. The high-value products garnered under this project are not easily prepared through competing technologies such as allylic substitution. The methods development outlined in this application along with the accompanying mechanistic investigations may begin to address long-standing challenges in enantioselective hydrofunctionalization technologies and lay the groundwork for related future studies. The educational outreach focuses on increasing public understanding and appreciation for catalysis via production and distribution of a collection of short videos, relating how synthetic catalytic chemistry has shaped the modern world. These videos are available on YouTube.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Steven Malcolmson教授的项目。Malcolmson教授是杜克大学化学系的教员。新化学反应的发展对于许多关键技术的持续进步至关重要，包括材料，农业和制药。发展合成方法的需要包括使用廉价和丰富的起始材料，同时产生最少的化学废物。一个有趣的反应，称为催化加氢官能化，增加了新的能力，改变容易获得的分子。加氢官能化反应目前在可使用的分子类型以及整个过程的速度和选择性方面受到限制。为了解决这些限制，Malcolmson实验室正在开发一些新的氢官能化反应，形成碳-碳和碳-氮键。这些反应利用了市售试剂和容易获得的起始材料，并且它们将来自所有试剂的所有原子并入产物中（原子经济性），同时使用最少的溶剂。因此，这些反应产生的化学废物很少。从反应中产生的产物是有价值的，因为它们可以用作精细化学、农业化学和药物化学工业中使用的合成结构单元。除了这项工作，Malcolmson博士和他的团队正在开发一系列简短的在线视频，以教育公众和本科生和研究生关于催化反应的发展如何通过工业应用塑造现代世界。这一努力提高了公众的科学素养，培养了预科生和大学生对科学的兴趣，同时也扩大了研究生教育，从而有助于培养下一代科学家。在化学部化学合成计划的资助下，杜克大学的Malcolmson实验室正在开发一些无环1，3-二烯，包括具有挑战性的内部二烯。具有手性螯合P，N-配体的钯基催化剂允许在室温下在短的反应时间内进行廉价、丰富且可商购的胺和β-二羰基亲核试剂的高效和对映选择性反应。二烯的氢官能化提供了一种方便和100%原子经济的方式来构建具有烯丙基立体中心的化合物，这是用于组装精细化学品、农用化学品和药物的有价值的结构单元。在该项目下获得的高价值产品不容易通过竞争性技术（如烯丙基取代）制备。本申请中概述的方法开发沿着伴随的机理研究可以开始解决对映体选择性加氢官能化技术中的长期挑战，并为相关的未来研究奠定基础。教育宣传的重点是通过制作和分发一系列短视频，提高公众对催化的理解和欣赏，这些视频讲述了合成催化化学如何塑造了现代世界。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。