Organic electrochemistry and radical/radical ion chemistry / Électrochimie organique et chimie des radicaux/radicaux ions

我的研究的主要目的是确定影响反应性中间体（自由基，自由基离子和化学吸附氢（Hads））的反应性的因素，并在分子水平上理解这些因素如何影响它们的反应性。 I.酰胺基自由基的反应性。我们将合成新的模型前体的环状酰胺约束反应在π电子状态（不成对的电子-在π轨道）和前体允许比较的π和西格玛（不成对的电子-在平面上的西格玛债券）状态的反应性。 二. N-取代内酰胺的环加成我们发现，光解N-氯-和N-O-甲磺酰基-内酰胺（6-和7-元环）得到相应的环收缩的氮杂环与100%保留的配置在迁移的碳。拟议的研究将涉及：机理研究（在内酰胺环的不同位置的取代基的影响，环的构象偏差，和同位素标记）;一般合成的N-羟基内酰胺的发展; N-氨基内酰胺的合成和重氮化; N-杂环天然产物的合成应用。三.有机电化学3a.硝基自由基阴离子的裂解。我们将通过电还原产生一系列1-硝基环丙烷/环丁烷和1-硝基环丙烷/环丁烷的自由基阴离子。在1位和2位具有各种取代基的（4-硝基苯基）-环丙烷/环丁烷（烷基，给电子/吸电子基团）并确定裂解的类型（均裂与异裂）和它们的裂解速率，使用循环伏安法（用于非常快速裂解的均相氧化还原催化）、库仑法和制备电解（产物鉴定）。3b.电催化加氢（ECH）。有机化合物的ECH涉及Hads（通过水的还原在电极表面上产生）与吸附的有机底物的反应。对单晶的表面和动力学研究旨在i）鉴定/理解影响效率和选择性的因素，ii）鉴定在氢化中具有活性的H（ads）的性质，和iii）确定电催化剂和反应条件如何影响速率（氢化与H解吸）。

The main objective of my research is to identify factors which influence the reactivity of reactive intermediates (radicals, radical ions, and chemisorbed hydrogen (Hads)), and to comprehend at the molecular level, how these factors affect their reactivity. I. REACTIVITY of amidyl radicals.- We will synthesize new model precursors of cyclic amidyls constrained to react in the pi electronic state (unpaired e- in a pi orbital) and precursors allowing to compare the reactivity of the pi and sigma (unpaired e- in the plane of the sigma bonds) states. II. RING CONTRACTION of N-substituted lactams.- We discovered that photolysis of N-chloro- and N-Omesyl-lactams (6- and 7-membered ring) gives the corresponding ring-contracted nitrogen heterocycle with 100% retention of configuration at the migrating carbon. The proposed research will involve: mechanistic studies (influence of substituents at various positions of the lactam ring, of the conformational bias of the ring, and of isotopic labelling); development of general syntheses of N-hydroxylactams; synthesis and diazotation of N-aminolactams; applications to the synthesis of N-heterocyclic natural products. III. ELECTROORGANIC CHEMISTRY.- 3a. Cleavage of nitro radical anions.- We will generate, by electroreduction, the radical anion of a series of 1-nitrocyclopropanes / cyclobutanes and 1-(4-nitrophenyl)-cyclopropanes / cyclobutanes having various substituents at positions 1 and 2 (alkyl groups, electron-donating /-attracting groups) and determine the type of cleavage (homolytic vs. heterolytic) and their rate of cleavage using cyclic voltammetry (homogeneous redox catalysis for very rapid cleavage), coulometry and preparative electrolysis (product identification). 3b. ElectroCatalytic Hydrogenation (ECH).- ECH of an organic compound involves reaction of Hads (generated on the electrode surface by reduction of water) with the adsorbed org. substrate. Surface and kinetic studies on single crystals aims at i) identifying / understanding the factors influencing the efficiency and selectivity, ii) identifying the nature of H(ads) active in hydrogenation, and iii) determining how the electrocatalyst and reaction conditions affect the rates (hydrogenation vs. H desorption).