SusChEM: CAREER: Catalytic Methods for Hydrofunctionalization of Unsaturated Compounds

SusChEM：职业：不饱和化合物氢官能化的催化方法

• 批准号: 1254636
• 负责人: Gojko Lalic
• 金额: $ 65万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-05-01 至 2018-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1254636&HistoricalAwards=false
• 关键词: SusChEM; CAREER; Catalytic; Methods; Hydrofunctionalization

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.

NSF化学司的化学催化计划支持华盛顿大学Gojko Lalic教授的研究工作，以调查使用过渡金属催化的非饱和化合物加氢功能化的新一般策略。 该研究小组首先研究了高度选择性铜催化的炔烃对烯烃的还原。 这种实用的方法避免了常见的副反应，例如过度还原和烯烃异构化。 末端炔烃的铜催化抗马科夫尼科夫氢化反应也正在研究中。 这些用于制备烷基溴化物制备的新催化反应为当前用于合成该类化合物的化学计量方法提供了有价值的替代方法。 Lalic教授的铜催化化学的第三个目的是通过炔烃的氢烷基化Z-和E-Alkenes的合成。 最后，研究小组正在研究一种基于金性艾伦的金催化的水功能化的Quaternary立体中心的不对称合成的新一般方法。 使用这种方法，研究了新方法，用于合成富含四氢呋喃的对映体，四氢呋喃，铬酸盐，吡咯，吡咯，哌啶，以及各种含有Quaternary立体相称物的碳纤维的研究。 除了提供有机合成的有价值的工具外，Lalic教授还积极通过为嘉宾讲座和参加学校科学博览会和西雅图地区科学的展览来促进两所当地高中的STEM教育。 将三键选择性减少到双键是有机化学中的常见且重要的转变。 目前，使用重量钯催化剂（Lindlar催化剂）实现了这些反应，这使其非常昂贵。 此外，当前的转换可能是不可预测的 - 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或大量废物形成，并且需要再次分离和处置，并再次增加与商业过程相关的材料和能源的增加。 Lalic教授及其小组在华盛顿大学正在准备新的，相对便宜的铜催化剂，这些催化剂将取代钯的选择性转换三键（Alkyne Compounds），以双键（烯烃化合物）（烯烃化合物）。 这些反应尤其重要，因为它们使用了丰富的金属，这些金属可为有机化合物以及在药物和药品以及其他精细化学物质中很重要的有机化合物提供可靠和可持续的访问。 除了为学生提供有机合成方面的出色实验室培训外，Lalic博士还建立并维护了有机和有机金属化学问题的数据库，该数据库可供学术界使用。 Lalic教授旨在通过为科学丰富计划做出贡献来解决少数民族和妇女在科学中的非代表性参与。 这些努力 - 西西雅图高中和英格拉汉高中的来宾演讲，参加汉密尔顿国际中学科学博览会，并参加西雅图地区科学展览，名为《太平洋科学中心》和《华盛顿大学》的名为《爪子科学》 - 在小学和中学生中促进化学作为职业选择。