Transfer Hydrogenative Hydroaminoalkylation and Imine Addition

转移氢化氢氨基烷基化和亚胺加成

• 批准号: 1265504
• 负责人: Michael Krische
• 金额: $ 48万
• 依托单位: University of Texas at Austin
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-10-01 至 2016-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1265504&HistoricalAwards=false
• 关键词: Transfer; Hydrogenative; Hydroaminoalkylation; Imine; Addition

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Michael J. Krische of the Department of Chemistry and Biochemistry at the University of Texas at Austin will explore new strategies for the formation of C-C bonds via hydroaminoalkylation. In such processes, hydrogen exchange between amines and pi-unsaturated reactants generates transient imine-organometal pairs that combine to form products of imine addition in the absence of stoichiometric byproducts. Unlike classical imine additions, direct amine-unsaturated C-C couplings (a) bypass discrete preparation of stoichiometric main-group organometallics and, consequently, circumvent generation of molar quantities of metallic waste, and (b) avoid discrete imine formation to enhance step-economy. These studies could offer more efficient, byproduct-free routes to important commodity chemicals (plastics, foams, pharmaceutical and agrochemicals) through the direct C-C coupling of basic chemical feedstocks. Byproduct-free catalytic methods for chemical manufacturing eliminate chemical waste at the source and, hence, are environmentally benign. In addition, this project will provide excellent training of students, from pre-undergraduate to post-doctoral, including those from groups historically underrepresented in the sciences.

在这个由化学部化学合成项目资助的项目中，德克萨斯大学奥斯汀分校化学与生物化学系的Michael J. Krische教授将探索通过氢氨烷基化形成C-C键的新策略。在此类过程中，胺和π-不饱和反应物之间的氢交换产生瞬时亚胺-有机金属对，这些对在不存在化学计量副产物的情况下结合形成亚胺加成产物。与经典的亚胺添加不同，直接胺-不饱和C-C偶联（a）绕过了化学计量主族有机金属的离散制备，因此避免了摩尔量金属废物的产生，并且（b）避免离散亚胺形成以增强步骤经济性。这些研究可以通过基本化学原料的直接 C-C 偶联，为重要的商品化学品（塑料、泡沫、药物和农用化学品）提供更有效、无副产品的路线。用于化学制造的无副产物催化方法从源头消除了化学废物，因此对环境无害。 此外，该项目将为从本科预科到博士后的学生提供出色的培训，包括来自历史上在科学领域代表性不足的群体的学生。