Beyond Acylation: New Methodology and Mechanistic Studies of Anhydrides for Stereoselective Synthesis

超越酰化：用于立体选择性合成的酸酐的新方法和机理研究

基本信息

批准号：
1764309
负责人：
Jared Shaw
金额：
$ 45万
依托单位：
University of California-Davis
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-07-15 至 2023-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764309&HistoricalAwards=false
关键词：
Beyond Acylation New Methodology Mechanistic

项目摘要

The Chemical Synthesis Program of the NSF Division of Chemistry supports this research project in the laboratory of Professor Jared Shaw in the Chemistry Department at the University of California, Davis. Professor Shaw discovers new reactions that enable simple, chemical starting materials to be converted into complex molecules with control of their overall shape. To accomplish this, Professor Shaw and his students are exploring three under explored modes of chemical reactivity. Each of these use a well-known molecular fragment, an anhydride, in a new way. The new reactions involve both the development of the new methods and an exploration of the factors that control the speed and specificity of the new reactions. Professor Shaw is the founding host of the Davis Science Cafe, which is a monthly event that brings scientists together to describe their work to the general public. This project support efforts to maximize the impact of the Science Cafe and other outreach events and bolster the spread of science communication in Northern California. This project also supports an array of outreach activities to achieve the goal of science education at all levels, including participation in a science fair at an elementary school, work with middle and high school students at Chemistry Camp for the Blind, and the revival of the Chapter of the Society for the Advancement of Chicanos/Latinos and Native Americans in Science (SACNAS) at UC Davis. This research may provide new, innovative approaches and advanced manufacturing opportunities for the chemical industry. Although the chemistry of anhydrides is dominated by their ability to serve as electrophilic acylating agents, new advances in the Shaw group exploit the ability of these compounds to serve as versatile nucleophiles. This project is pursuing three specific avenues of inquiry. First, the addition of anhydrides to alpha-chiral imines has shown stereocontrol that defy the rules established for carbonyl compounds. A broad investigation of the outcomes of these reactions paired with computational studies is being used to build a new stereochemical model to describe the behavior of imines in reactions with soft nucleophiles, i.e. electron-rich alkenes. Second, the base-mediated and, if possible, catalyzed reactions of anhydrides with new electrophiles are being studied. This effort involves the synthesis of a new class of chiral catalysts and the development of addition reactions between anhydrides and electron-deficient alkenes and aziridines. Third, the reactions of anhydride enol silanes is being nvestigated. Although a small number of these compounds have been made, the Shaw group has discovered new organocatalytic reactions that enable the reactivity to be steered toward at least two different products with the same imine electrophile. This investigation complements previous work examining the reactions of imines with anhydrides by providing novel reactivity leading to new and interesting products.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

NSF化学部的化学综合计划在加利福尼亚大学戴维斯分校的化学系贾里德·肖教授实验室中支持该研究项目。 Shaw教授发现了新反应，使简单的化学起始材料能够通过控制其整体形状转化为复杂的分子。为此，Shaw教授和他的学生正在探索三种化学反应性模式。这些都以新的方式使用了众所周知的分子片段，即赤道。新反应既涉及新方法的发展，又涉及控制新反应速度和特异性的因素。 Shaw教授是Davis Science Cafe的创始主持人，这是一个每月一次的活动，将科学家们汇集在一起，将他们的工作描述给公众。该项目支持最大程度地发挥科学咖啡馆和其他外展活动的影响，并加强北加州科学传播的传播。该项目还支持一系列的外展活动，以实现各个层次的科学教育的目标，包括在一所小学的科学博览会上与盲人化学训练营的中学和高中生一起工作，以及在UC Davis的Chicanos/Latinos和Americanans Americanans和Americanans Science of Americanans of Americanans of Americanans of Americanans of Americanans of Chip Americans and Americanans of uc davis of uc davis of Chicanos/Latinos促进学会的复兴。这项研究可能为化学工业提供新的创新方法和先进的制造机会。尽管酸酐的化学因素以它们充当亲电酰基化剂的能力为主，但Shaw组的新进步利用了这些化合物作为多功能亲核试剂的能力。该项目正在追求三个特定的查询途径。首先，在α-手术亚胺中添加了赤霉素已显示出立体控制，这无视针对羰基化合物制定的规则。对这些反应与计算研究的结果进行的广泛研究正在用于构建一个新的立体化学模型，以描述在具有软核寄生机的反应中，即富含电子的烷烃的反应中的行为。其次，研究了基础介导的，如果可能的话，正在研究酸酐与新电力物的催化反应。这项工作涉及合成一类新的手性催化剂，以及酸酐和电子缺陷型烷烃和氮嘧啶之间的添加反应的发展。第三，正在对酸酐烯醇硅烷的反应进行NVESTIND。尽管已经制成了少数这些化合物，但邵氏基团发现了新的有机催化反应，使反应能够至少朝着具有相同的亚胺电力的至少两种不同的产物。这项调查补充了以前的工作，通过提供新颖有趣的产品的新反应性来检查亚胺对酸酐的反应。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子和更广泛影响的评估评估的评估来支持的。

项目成果

期刊论文数量（7）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Acyclic Stereocontrol in the Additions of Nucleophilic Alkenes to α‐Chiral N ‐Sulfonyl Imines

亲核烯烃与手性 N 磺酰亚胺加成的非环立体控制

DOI：
10.1002/chem.201902790
发表时间：
2019
期刊：
Chemistry – A European Journal
影响因子：
0
作者：
Moore, Lucas C.;Lo, Anna;Fell, Jason S.;Duong, Matthew R.;Moreno, Jose A.;Rich, Barry E.;Bravo, Martin;Fettinger, James C.;Souza, Lucas W.;Olmstead, Marilyn M.
通讯作者：
Olmstead, Marilyn M.

Organocatalytic Mukaiyama Mannich Reactions of 2,5-Bis(trimethylsilyloxy)furan