SusChEM: CAREER: Catalytic Methods for Hydrofunctionalization of Unsaturated Compounds

NSF化学部的化学催化计划支持华盛顿大学的Gojko Lalic教授的研究工作，以研究使用过渡金属催化的不饱和化合物的加氢官能化的新的一般策略。 该研究小组首先研究了高选择性的铜催化还原炔烃为烯烃。 这种实用的方法避免了常见的副反应，如过度还原和烯烃异构化。 铜催化的末端炔的反马氏溴氢化反应也在研究中。 这些用于制备烯基溴的新催化反应为目前用于合成这类化合物的化学计量方法提供了有价值的替代方案。 Lalic教授铜催化化学的第三个目标是通过炔的加氢烷基化合成Z-和E-烯烃。 最后，该研究小组正在研究一种新的通用方法，以不对称合成季立体中心的基础上金催化氢官能化的手性联烯。 使用这种方法，用于合成对映体富集的四氢呋喃，四氢吡喃，色满，吡咯，哌啶，和各种含有季立体中心的碳环的新方法正在研究中。 除了为有机合成提供有价值的工具外，Lalic教授还积极促进当地两所高中的STEM教育，为客座讲座做出贡献，并参加学校科学博览会和西雅图地区的科学展览。 三键选择性还原为双键是有机化学中常见而重要的转化反应。 这些反应目前使用5重量%的钯催化剂（Lindlar催化剂）来实现，这使得其非常昂贵。 此外，当前的转化可能是不可预测的-导致形成不需要的单键（烷烃化合物），因此必须密切监测反应以实现高水平的产物形成，否则将形成大量的废物并需要分离和处理，这再次增加了与商业方法相关的材料和能量的成本。 华盛顿大学的Lalic教授和他的研究小组正在制备新的、相对便宜的铜催化剂，这种催化剂将在三键（炔化合物）向双键（烯化合物）的选择性转化中取代钯。 这些反应特别重要，因为它们使用地球上丰富的金属，这些金属提供了可靠和可持续的有机化合物，这些化合物在药物和制药以及其他精细化学品中很重要。 除了为他的学生提供有机合成方面的优秀实验室培训外，Lalic博士还建立并维护了一个可供学术界使用的有机和有机金属化学问题数据库。 教授Lalic旨在解决少数民族和妇女在科学中的非代表性参与，为科学丰富计划做出贡献。 这些努力--在西西雅图高中和英格拉哈姆高中的客座讲座，参加汉密尔顿国际中学科学博览会，以及参加太平洋科学中心和华盛顿大学的西雅图地区科学展览“科学之爪”--促进了小学生和中学生的职业选择。

The Chemical Catalysis Program of the NSF Division of Chemistry supports the research efforts of Professor Gojko Lalic of the University of Washington to investigate new general strategies for the hydrofunctionalization of unsaturated compounds using transition metal catalysis. The research group is first studying the highly selective copper-catalyzed reduction of alkynes to alkenes. This practical method avoids common side reactions such as over-reduction and alkene isomerization. Copper-catalyzed anti-Markovnikov hydrobromination reactions of terminal alkynes are also under investigation. These new catalytic reactions for the preparation of alkenyl bromides provide valuable alternatives to stoichiometric methods currently used for the synthesis of this class of compounds. A third aim of Professor Lalic's copper-catalyzed chemistry is the synthesis of Z- and E-alkenes via the hydroalkylation of alkynes. Finally, the research group is investigating a new general approach to the asymmetric synthesis of quaternary stereocenters based on gold-catalyzed hydrofunctionalization of chiral allenes. Using this approach, new methods for the synthesis of enantioenriched tetrahydrofurans, tetrahydropyrans, chromans, pyrroles, piperidines, and a variety of carbocyles containing quaternary stereocenters are under investigation. In addition to providing valuable tools for organic synthesis, Prof. Lalic is active in promoting STEM education at two local high schools by contributing to guest lectures and participating in school science fairs and in Seattle-area science exhibits. The selective reduction of triple bonds to double bonds is a common and important transformation in organic chemistry. These reactions are currently achieved using a 5% by weight palladium catalyst (Lindlar catalysts) which makes it very expensive. Furthermore, the current transformations can be unpredictable - leading to the formation of unwanted single bonds (alkane compounds) and so the reaction must be closely monitored to achieve high levels product formation or a significant amount of waste will form and need to be separated and disposed of, again, increasing the cost of materials and energy associated with the commercial processes. Professor Lalic and his group at the University of Washington are preparing new, relatively inexpensive, copper catalysts that will take the place of palladium in the selective conversion of triple bonds (alkyne compounds) to double bonds (alkene compounds). These reactions are especially important because they use earth abundant metals which provide reliable and sustainable access to organic compounds which are important in medicines and pharmaceuticals as well as in other fine chemicals. In additional to providing his students with excellent laboratory training in organic synthesis, Dr. Lalic has established and maintained a database of problems in organic and organometallic chemistry that is available to the academic community. Professor Lalic seeks to address non-representative participation of minorities and women in science by contributing to science enrichment programs. These efforts - guest lectures at West Seattle High School and Ingraham High School, participation in the Hamilton International Middle School Science Fair, and participation in the Seattle-area science exhibit called Paws on Science at the Pacific Science Center and the University of Washington - promote chemistry as a career choice among elementary and middle school students.