Synthesis of chiral diene systems via ring closing enyne metathesis and their applications in diels-alder reactions

Çayır, Merve
The main subject of this thesis is synthesis of chiral diene systems via Ring Closing Enyne Metathesis (RCEM). Furan and thiophene carbaldehydes were chosen as starting compounds. As a result of allylation and propargylation reaction of these aldehydes targeting racemic heteroaryl substituted homoallylic and homopropargylic alcohols were synthesized. Enantiomerically enriched alcohols were obtained by enzymatic resolution method with different enzymes (PS-II, Lipozyme) with the high enantiomeric excess values. Absolute configurations of all alcohols are known. O-allylation and O-propargylation reactions of enantiomerically pure alcohols, afforded feasible enyne units for RCEM were synthesized successfully. All RCEM reactions were performed by using Grubbs‟ 1st generation catalyst. The absolute configuration of all chiral diene systems were known since during the course of the all reactions, configurations were preserved. As a last step, Diels-Alder reactions were applied to some of these chiral diene systems to get bicyclic compounds and comment on the stereoselectivity. Only one diastereomeric cycloadduct was observed as a result of Diels-Alder applications.


Synthesis and biological evaluation of optically active conjugated gamma- and delta-lactone derivatives
ŞARDAN, Melis; Sezer, Serdar; GUNEL, Aslihan; AKKAYA, MAHİNUR; Tanyeli, Cihangir (2012-09-15)
An efficient synthesis of racemic and both enantiomeric forms of heteroaryl substituted gamma- and delta-lactone derivatives derived from allyl and homoallyl alcohol backbones has been accomplished via ring closing metathesis reaction. 2-Heteroaryl substituted allyl and homoallyl alcohols have been efficiently resolved through enzymatic method with high ee (97-99%) and known stereochemistry. Antimicrobial and antioxidant activities of target lactones were evaluated.
Synthesis of ferrocenyl quinolines
Zora, Metin (Elsevier BV, 2008-06-01)
A convenient one-pot synthesis of ferrocenyl-substituted quinolines via a molecular iodine-catalyzed reaction of ferrocenylimines with enolizable aldehydes is reported. First, nucleophilic addition of the in situ generated enol to ferrocenylimine produces beta-anilinopropionaldehyde, which then undergoes intramolecular Friedel-Crafts reaction to give dihydroquinoline derivative. Finally, subsequent dehydration and aerobic oxidation affords ferrocenyl quinolines.
Synthesis of conducting block and graft copolymers with polyether segments
Yagci, Y; Toppare, Levent Kamil (Wiley, 2000-07-01)
Synthesis of block and graft copolymers containing polyether and conducting polypyrrole sequences were described. Pyrrole moieties were incorporated at the chain ends of polytetrahydrofuran and polysiloxane and at the side chains of polyethyl vinylether by ionic polymerization and appropriate chemical reactions. Subsequent electropolymerization with pyrrole through these moities yielded free standing films of the corresponding block and graft copolymers. The formation copolymers was evidenced by FTIR spectr...
Synthesis of Cyano-Substituted Diaryltetracenes from Tetraaryl[3] cumulenes**
GAWEL, Przemyslaw; Dengiz, Çağatay; FINKE, Aaron D.; TRAPP, Nils; BOUDON, Corinne; GISSELBRECHT, Jean-Paul; DIEDERICH, Francois (2014-04-22)
A versatile, two-step synthesis of highly substituted, cyano-functionalized diaryltetracenes has been developed, starting from easily accessible tetraaryl[3]cumulenes. This unprecedented transformation is initiated by [2+2] cycloaddition of tetracyanoethylene (TCNE) to the proacetylenic central double bond of the cumulenes to give an intermediate zwitterion, which after an electrocyclization cascade and dehydrogenation yields 5,5,11,11-tetracyano-5,11-dihydrotetracenes in a one-pot procedure. A subsequent c...
Asymmetric synthesis of chiral camphor fused pyridine type novel organocatalysts
Küçükdişli, Murat; Tanyeli, Cihangir; Department of Chemistry (2009)
Chiral pyridines as organocatalysts have been used in asymmetric organic synthesis in recent years. The asymmetric synthesis of camphor fused pyridine type novel organocatalysts were perfomed starting from cheap and easily available natural (+)-camphor. Using camphor fused pyridine skeleton, six organocatalysts 29, 32, 33, 38, 40, and 41were successfully synthesized. The first four nucleophilic and Lewis base catalysts 29, 32, and 33 are different P-oxides and P,N-dioxides which were tested in allylation of...
Citation Formats
M. Çayır, “Synthesis of chiral diene systems via ring closing enyne metathesis and their applications in diels-alder reactions,” M.S. - Master of Science, Middle East Technical University, 2010.