UNIGE document Doctoral Thesis
previous document  unige:18222  next document
add to browser collection
Title

One point binding chiral ruthenium Lewis acid catalysts: asymmetric intramolecular Diels-Alder reactions and conformational studies

Author
Director
Defense Thèse de doctorat : Univ. Genève, 2011 - Sc. 4391 - 2011/11/25
Abstract Half-sandwich chiral electron poor one-point binding ruthenium catalyst that I focused on was one of the research interests in the Kündig group. A more general aim was to apply these catalysts to new transformations, expanding the range of applications that these complexes can satisfactorily catalyze. Only one successful example of asymmetric type 2 IMDA cycloaddition was reported. The challenges arise from the facts that several inconsistencies remain in the reported structure assignment of ledol. We therefore employed the crucial intermediate for the first total synthesis of ent-ledol to provide in good yield with excellent ee. The conformational studies of Ru-dienophile complexes with NOESY and ROESY experiments revealed a conformationally coordinate structure with correlations between dienophile protons and Cp/Indenyl ‘roof’ or chiral BIPHOP-F ligand protons of catalyst part. These NMR results helped to explain the ground state conformations in solution that probably correspond to the observed enantioselectivity in DA reactions.
Keywords One-point binding ruthenium catalystAsymmetric catalysisIntramolecular Diels-Alder reactionEnt-Ledol
Identifiers
URN: urn:nbn:ch:unige-182226
Full text
Thesis (11.9 MB) - public document Free access
Structures
Citation
(ISO format)
THAMAPIPOL, Sirinporn. One point binding chiral ruthenium Lewis acid catalysts: asymmetric intramolecular Diels-Alder reactions and conformational studies. Université de Genève. Thèse, 2011. https://archive-ouverte.unige.ch/unige:18222

270 hits

561 downloads

Update

Deposited on : 2012-01-30

Export document
Format :
Citation style :