CAREER: New Catalysts and Methods for Amine Synthesis via Stereoselective Allene Aziridination

有了这个职业奖，化学系的合成和催化项目支持了威斯康星大学麦迪逊分校的詹妮弗·M·舒梅克教授的研究。Schomaker教授将开发新的联烯氧化方法，以便快速灵活地合成复杂的、富含对映体和密集官能化的胺基序，这些基序是天然产物、催化配体和生物过程探针的重要组成部分。该项目的第一个目标是开发可靠的方法，用于区域和立体控制的丙烯氮杂化反应，以制备反应性双环亚甲基氮杂环丙烷支架。其次，将开发将这些关键中间体转化为胺化立体三元化合物(包含三个连续的含杂原子手性碳的化合物)的方法，从而提供用于合成的各种含氮构建块的途径。最后，本项目的第三个目标是将联烯氮杂环化反应应用于交替霉素的合成。交替霉素是一种复杂的氨基环戊醇，具有很强的抗菌、抗肿瘤、抗原虫和抗疟疾活性。越来越多的化学和立体选择性催化的需要为新的合成有机方法的发展提出了令人兴奋的挑战。Schomaker的工作将为化学选择性构建碳-氮键确定新的催化范例。这些新的催化模式将使合成生物相关分子的有效方法成为可能。她的工作的更广泛的影响将通过与威斯康星大学麦迪逊分校的人员计划(大学前卓越学习丰富机会计划)合作实现。她将在高中生涯的早期识别当地经济困难的学生，并为专注于开发新的合成方法的研究经验提供指导机会。学生将有充足的时间发展宝贵的实验室技能，学习以口头和书面形式进行科学交流，并参加研讨会，以扩大他们对研究在解决重要社会问题方面所起的作用的理解。学生们还将利用社交媒体跟踪他们的进步，并与家人、朋友和同学分享他们的经历。

With this CAREER Award, the Chemistry Division's Synthesis and Catalysis programs are supporting the research of Professor Jennifer M. Schomaker of the University of Wisconsin-Madison. Professor Schomaker will develop new allene oxidation methodologies to permit the rapid and flexible syntheses of complex, enantioenriched and densely functionalized amine motifs that are important components of natural products, ligands for catalysis and probes of biological processes. The first goal of this project is to develop reliable methods for regio- and stereocontrolled allene aziridination to reactive bicyclic methylene aziridine scaffolds. Second, methods to transform these key intermediates into aminated stereotriads (compounds containing three consecutive heteroatom-bearing chiral carbons) will be developed, providing access to a diverse array of nitrogen-containing building blocks for synthesis. Finally, the third goal of this project is to apply allene aziridination to the synthesis of jogyamycin, a complex aminocyclopentitol exhibiting potent antibiotic, antitumor, antiprotozoal and antimalarial activities. The need for increasingly chemo- and stereoselective catalysis presents exciting challenges for the development of new synthetic organic methodologies. Schomaker's work will identify new paradigms in catalysis for the chemoselective construction of carbon-nitrogen bonds. These new modes of catalysis will enable powerful approaches to the synthesis of biologically relevant molecules. The broader impacts of her work will be realized through collaboration with the PEOPLE program (Pre-College Enrichment Opportunity Program for Learning Excellence) at UW-Madison. She will identify economically disadvantaged local students early in their high school careers and provide mentored opportunities for research experiences focusing on the development of new synthetic methodologies. Students will have ample time to develop valuable laboratory skills, learn to communicate scientifically in both oral and written forms and participate in seminars to broaden their understanding of the role research plays in addressing important societal concerns. Students will also employ social media to track their progress and share their experiences with family, friends and classmates.