Diels-Alder reaction of heterocyclic imine dienophiles

摘要: This thesis describes mechanistic studies, rational ligand design, and synthesis of asymmetric transition metal catalysts. The topics addressed concerned [Papers I-VII]:[I] addition diethyl zinc to N-(diphenylphosphinoyl)benzalimine catalyzed by bicyclic 2-azanorbornyl-3-methanols was studied. An efficient route both diastereomers new with an additional chiral center developed, in the best case 97% ee obtained these ligands. experimental results were rationalized a computational DFT-study.[II] aza-Diels-Alder reaction cyclopentadiene heterocyclic imines derived from (S)-1-phenylethylamine different heteroaromatic aldehydes developed. cycloaddition proved be highly diastereoselective offers very rapid access possible biologically active compounds interesting precursors for (P,N)-ligands. [III] A convenient high-yielding method preparation (R)-tolterodine, utilizing catalytic Me-CBS reduction Highly enantio-enriched (R)-6-methyl-4-phenyl-3,4-dihydrochromen-2-one (94% ee) recrystallized yield practically enantiopure material (ee >99%) converted (R)-tolterodine four-step procedure. [IV] mechanism iridium-phosphanooxazoline-catalyzed hydrogenation unfunctionalized olefins has been studied means DFT-calculations (B3LYP) kinetic experiments. calculations suggest that involves unexpected IrIII-IrV cycle facilitated coordination second equivalent dihydrogen. On basis proposed cycle, performed on full system 88 atoms. These also used explain enantioselectivity displayed catalyst.[V VI] class (P,N)-ligands Ir-catalyzed aryl alkenes ligands tolerate broad range substrates. enantiomeric excesses are, so far, reported can using selectivity model.[VII] complex formed between quincorine-amine, containing primary quinuclidine amino function, [Cp*RuCl]4 catalyzes aromatic aliphatic ketones up 90% approx. 24-times faster than previously Ru-diamine complexes. reason lower but opposite stereoselectivity seen quincoridine-amine, as compared study mechanism. theoretical revealed significantly activation barrier alcohol mediated split dihydrogen, non-alchol process. finding importance diphosphine/diamine enantioselective ketones.