Expanding the Scope of Donor/Acceptor Carbenoids

扩大供体/受体类胡萝卜素的范围

• 批准号: 1465189
• 负责人: Huw Davies
• 金额: $ 42万
• 依托单位: Emory University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1465189&HistoricalAwards=false
• 关键词: Expanding; Scope; Donor; Acceptor; Carbenoids

With this award, the Chemical Synthesis program is supporting fundamental research of Professor Huw M. L. Davies at Emory University. Professor Davies and his students will employ chiral catalysts for the development of new enantioselective methods in organic synthesis. The study explores reactions induced by vinylogous reactions of metal-stabilized vinylcarbenes and has the potential of generating entirely new transformations in an enantioselective manner. The vinylogous reactions of vinylcarbenes are not yet well understood and these studies are expected to contribute to the fundamental understanding of rhodium carbene chemistry. Professor Davies will integrate the research and educational components of this project within several new initiatives for developing a collaborative and supportive environment for academic researchers. A new Chemistry Research & Diversity Program is planned which will bring professors from minority universities with 2 of their students to work on summer research projects. A robust student-mentoring plan has been designed to ensure the students become experts in their specific area of research and develop the breadth of experience and the communication skills necessary to be highly effective in their future careers. Professor Davies has developed many outreach activities available to his students such as the Spelman Journal Club, science cafes, the Atlanta Science Festival, Chemical Innovator Lecture Series, videoconference short courses, and career development lectures by visiting industrial speakers. In this research, synthetic transformations of metal vinylcarbenes, proceeding by an initial reaction occurring at the vinylogous position of the vinylcarbene, will be explored. Methods will be developed to control the site of reactivity of the metal vinylcarbenes by using either gold catalysts or sterically bulky dirhodium catalysts. A number of novel stereoselective protocols of limited prior precedence will be examined, including [4+3] cycloadditions, [4+2] cycloadditions and crotylations, which will open up new possibilities for the rapid construction of complex target molecules.

通过这一奖项，化学合成项目支持埃默里大学休·M·L·戴维斯教授的基础研究。戴维斯教授和他的学生将使用手性催化剂来开发有机合成中的新的对映选择性方法。这项研究探索了由金属稳定的乙烯基卡宾的乙烯基卡宾引发的反应，并有可能以对映选择性的方式产生全新的转化。乙烯基卡宾的乙烯基反应还没有被很好地理解，这些研究有望有助于对Rh卡宾化学的基本理解。戴维斯教授将把这个项目的研究和教育部分整合到几个新的倡议中，为学术研究人员发展一个合作和支持的环境。一个新的化学研究和多样性项目正在计划中，该项目将邀请少数族裔大学的教授和他们的2名学生参与暑期研究项目。设计了一个强有力的学生辅导计划，以确保学生成为其特定研究领域的专家，并培养在未来职业生涯中高度有效所需的广泛经验和沟通技能。戴维斯教授为他的学生开发了许多推广活动，如斯佩尔曼杂志俱乐部、科学咖啡馆、亚特兰大科学节、化学创新者系列讲座、视频会议短期课程，以及来访的工业演讲者的职业发展讲座。在这项研究中，将探索金属乙烯基卡宾的合成转化，首先发生在乙烯基卡宾的乙烯基位上的初始反应。将开发方法来控制金属乙烯基卡宾的反应位置，要么使用金催化剂，要么使用空间大小较大的镝催化剂。我们将考察一些具有有限优先顺序的新型立体选择性方案，包括[4+3]环加成反应、[4+2]环加成反应和巴豆化反应，这将为快速构建复杂的靶分子开辟新的可能性。

项目成果

Rh(II)-Catalyzed Monocyclopropanation of Pyrroles and Its Application to the Synthesis Pharmaceutically Relevant Compounds

• DOI: 10.1021/acs.orglett.9b02250
• 发表时间: 2019-08-02
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Fu, Jiantao;Wurzer, Nikolai;Davies, Huw M. L.
• 通讯作者: Davies, Huw M. L.