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Constant Change: Experimental and Computational Studies toward an Understanding of how Reaction Dynamics Influence Chemical Transformations of Short-Lived Intermediates

不断变化：通过实验和计算研究了解反应动力学如何影响短寿命中间体的化学转化

基本信息

批准号：
251211948
负责人：
Professorin Dr. Julia Rehbein
金额：
--
依托单位：
Institut für Organische Chemie
依托单位国家：
德国
项目类别：
Independent Junior Research Groups
财政年份：
2014
资助国家：
德国
起止时间：
2013-12-31 至 2019-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/251211948?language=en
关键词：
Constant Change Experimental Computational Studies

项目摘要

The overall objective of our work is the development and application of modern physical-organic methods to answer questions related to synthetic-organic chemistry and chemical biology. Our intended contribution to a more complete understanding of the complex problem of selectivity and diversity in chemical reactions will focus especially on dynamic factors. To identify and describe dynamic effects that can take place on so called bifurcating potential energy surfaces (PESs) is our major motivation in studying (enzyme) catalyzed reactions. In detail cationic reaction cascades as they occur in terpene biosynthesis will be one major part of the proposed work schedule. Within this project mechanistic aspects will go along with methodological tasks in the design of efficient photolable precursors for carbenium ions. The other proposed work is settled in the area of NHC-catalysis where we found experimental and computational evidence of radical pathways. Under the premises that the occurrence of radical intermediates can be generalized our findings will be utilized in broaden the range of NHC-catalyzed reactions. All our studies are based on experimental and computational work and include synthesis, kinetic measurements by laser-flash-photolysis, time resolved IR and NMR as well as labeling studies. In terms of computational chemistry electronic structure calculations will be used in conjunction with molecular dynamics studies.In total the proposed projects are highly interdisciplinary, in the choice of methods and terms of content, as they unite aspects of organic and physical chemistry as well as chemical biology. This is not only an excellent opportunity for young scientist (Bachelor, Master, PhD) to broaden their expertise and to develop a unique scientific profile but also opens up opportunities for various collaborations with groups of the MIN faculty of the Universität Hamburg and related research facilities.

我们工作的总体目标是发展和应用现代物理有机方法来回答与合成有机化学和化学生物学有关的问题。我们对更全面地理解化学反应的选择性和多样性这一复杂问题的预期贡献将特别集中在动力学因素上。识别和描述可能发生在所谓的分岔势能面（PESs）上的动态效应是我们研究（酶）催化反应的主要动机。详细地说，发生在萜烯生物合成中的阳离子级联反应将是拟议工作计划的一个主要部分。在这个项目中，机械方面将与设计有效的可光性碳离子前体的方法学任务一起进行。另一项提议的工作是在nhc催化领域，在那里我们发现了自由基途径的实验和计算证据。在自由基中间体的发生可以普遍化的前提下，我们的发现将用于扩大nhc催化反应的范围。我们所有的研究都是基于实验和计算工作，包括合成、激光闪光光解动力学测量、时间分辨红外和核磁共振以及标记研究。在计算化学方面，电子结构计算将与分子动力学研究结合使用。总的来说，拟议的项目在方法的选择和内容方面都是高度跨学科的，因为它们结合了有机化学和物理化学以及化学生物学的各个方面。这不仅是年轻科学家（学士，硕士，博士）拓宽专业知识和发展独特科学形象的绝佳机会，而且还为与Universität汉堡的MIN教师团体和相关研究机构的各种合作提供了机会。