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

我们工作的总体目标是发展和应用现代物理-有机化学方法来回答与合成有机化学和化学生物学有关的问题。我们打算对更全面地理解化学反应中的选择性和多样性这一复杂问题作出贡献，特别是集中在动态因素上。识别和描述可能发生在所谓的分叉势能面(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，在萜类生物合成中发生的阳离子反应级联将是拟议的工作时间表的一个主要部分。在这个项目中，机械方面将伴随着设计有效的卡宾离子光解前体的方法学任务。另一项拟议的工作是在NHC催化领域，在那里我们发现了自由基路径的实验和计算证据。在自由基中间体的发生可以推广的前提下，我们的发现将被用于拓宽NHC催化的反应范围。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IR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，拟议的项目在方法和内容的选择上是高度跨学科的，因为它们结合了有机化学、物理化学和化学生物学的各个方面。这不仅是青年科学家(学士、硕士、博士)拓宽专业知识和形成独特的科学形象的绝佳机会，而且还为与汉堡大学最低教员小组和相关研究机构开展各种合作打开了机会。

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.