test_moissonnage_selune
type: Agent

Titanium complexes for the formation of nitrogen compounds : synthesis of homoallylamines and amidines
type: Distribution
access URL: https://theses.hal.science/tel-00674048
format: HTML
issued: 2026-05-27T00:35:30.663787
modified: 2026-05-27T00:35:30.420706

Titanium complexes for the formation of nitrogen compounds : synthesis of homoallylamines and amidines
type: Dataset
contact point: Organization
  fn: CCSD
keyword: diamidines-macrocyliques
keyword: allyltitanation
keyword: bisbenzotriazole-derivatives
keyword: amines-homoallyliques
keyword: dioxocyclams
keyword: titanium
keyword: cationic-2-aza--cope-rearrangement
keyword: homoallylic-amines
keyword: homocrotylamines
keyword: homoallylamines
keyword: titane
keyword: homoallyl-e-homocrotylamines
keyword: derives-benzotriazole
keyword: macrocyclic-diamidines
keyword: rearrangement-cationique-2-aza-cope
keyword: theses
keyword: derives-bisbenzotriazole
keyword: benzotriazole-derivatives
keyword: chimothechemical-sciencesother
keyword: infoeu-reposemanticsdoctoralthesis
keyword: dioxocyclames
landing page: https://theses.hal.science/tel-00674048
description: Homoallylic amines are key reagents for the formation of a large number of biologically interesting products. Due to the double bond of their allylic moiety, easily functionalisable, they are commonly used in organic synthesis. This research work deals with the synthesis of homoallylic amines thanks to titanium complexes. In fact, the reductive coupling between of imines and dienes promoted by titanium allows the formation of diastereoisomeric homoallylamines syn and anti. The diastereoselectivity of the reaction is directly affected by the nitrogen substituent. Whether it is benzyl or phenyl, the selectivity will be in favour of syn or anti respectively. Moreover, the addition of a the Lewis acid BF3.OEt2 not only considerably decreases the reaction time but also inverts the diastereoselectivity obtained with the reaction without a Lewis acid.The decomposition of homoallylamines during the purification process allowed to highlights a cationic 2-Aza-Cope rearrangement. This rearrangement was applied to the catalytic synthesis of homocrotylamines and of a _,_ unsaturated amino acid. This manuscript also reports the synthesis of homoallylamines by coupling between dienes and benzotriazole derivatives. These derivatives generate iminiums which react efficiently than imines to form the desired amines. Moreover, the reaction ran with bis(benzotriazole) derivatives lead selectively to homoallyl-(E)-homocrotylamines. This reactivity is explained by a triple cascade reaction meaning an allyltitanation - cationic 2-Aza-Cope rearrangement – allyltitanation.Secondly, part of this thesis focuses on the reaction between Ti(NMe2)4 complex and dioxocyclams to produce new macrocyclic diamidines. The chemical properties of this amidines present several interests for the formation of complexes with metals such as Cu, Ni and Pd. The analyses of the complexes deserve further investigation to determine unambiguously their structure in order to understand much better the coordination of …
identifier: NNT: 2011DIJOS026
issued: 2026-05-27T00:35:30.477248
language: fr
modified: 2026-05-27T00:35:30.477256