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

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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.