Show/Hide Menu
Hide/Show Apps
Logout
Türkçe
Türkçe
Search
Search
Login
Login
OpenMETU
OpenMETU
About
About
Open Science Policy
Open Science Policy
Open Access Guideline
Open Access Guideline
Postgraduate Thesis Guideline
Postgraduate Thesis Guideline
Communities & Collections
Communities & Collections
Help
Help
Frequently Asked Questions
Frequently Asked Questions
Guides
Guides
Thesis submission
Thesis submission
MS without thesis term project submission
MS without thesis term project submission
Publication submission with DOI
Publication submission with DOI
Publication submission
Publication submission
Supporting Information
Supporting Information
General Information
General Information
Copyright, Embargo and License
Copyright, Embargo and License
Contact us
Contact us
Synthesis of ferrocenyl cycloheptadienones
Download
index.pdf
Date
2005
Author
Açıkgöz, Canet
Metadata
Show full item record
Item Usage Stats
233
views
87
downloads
Cite This
Synthesis of seven-membered ring systems such as cycloheptadienones has attracted a great deal of attention in organic chemistry since they are present in a variety of biologically important molecules. Incorporation of the essential structures of such compounds with a ferrocene moiety instead of an aryl group could provide subtances with enhanced antitumor activities since some ferrocene derivatives have already proved to be active against a number of tumors. To develop a ferrocenyl-substituted seven-membered ring forming reaction, we have investigated the reaction of cyclopropylcarbene-molybdenum complex with ferrocenyl-substituted alkynes. As ferrocenyl-substituted alkyne, ferrocenylpropyne (25B), (2-ferrocenylethynyl)trimethylsilane (25C), 1-ferrocenyl-3-phenylprop-1-yne (25D), 1-ferrocenyl-2-phenylethyne (25E), diferrocenylethyne (25F), ferrocenyl(formyl)acetylene (25G) were synthesized starting from ethynylferrocene (25A). The reaction between cyclopropylcarbene-molybdenum complex and ferrocenyl alkynes produced ferrocenyl-substituted cycloheptadienones 26, hydrolysis product of cycloheptadienones, 27, ?-hydroxycycloheptadienones 28 and cyclobutenones 29, depending on the substitution pattern of the alkyne moiety. Interestingly, ?-hydroxycycloheptadienone product 28B was isolated from these types of reactions for the first time. Terminal alkynes, trimethyl- and formyl-substituted alkynes did not produce any expected product, possibly depending on the steric and electronic effects, and/or the polymerization of the alkyne. Proposed mechanism for the formation of cycloheptadienones involves metallacyclobutene formation, electrocyclic ring opening, electrocyclic ring closure, CO insertion, reductive elimination.
Subject Keywords
Chemistry, Organic
URI
http://etd.lib.metu.edu.tr/upload/3/12606365/index.pdf
https://hdl.handle.net/11511/15199
Collections
Graduate School of Natural and Applied Sciences, Thesis
Suggestions
OpenMETU
Core
Synthesis of chiral lactones via the baeyer villiger oxidation of cyclic aromatic acetoxy ketones novel annulation reactions of 2-propynyl-1,3-dicarbonyl compounds to form pyrroles addition of acyl phosphonates to diethyl cyanophosphonate (depc)
Aybey, Asuman; Demir, Ayhan Sıtkı; Department of Chemistry (2009)
Chiral Baeyer-Villiger (BV) oxidation of cyclic ketones allows rapid access to asymmetric lactones as valuable intermediates in organic chemistry and frequently encountered precursors in enantioselective synthesis. In the first part, BV oxidation of functionalized ketones, especially cyclic -hydroxy and acetoxy ketones is described which could be a straightforward route to the -hydroxy lactones and -hydroxyalkanoic acid derivatives. The -acetoxylation of indanone, tetralone and chromanone derivatives by usi...
Synthesis and enzymatic resolution of various cyclopentenoid and cyclohexenoid type compounds
İyigün, Çiğdem; Tanyeli, Cihangir; Department of Chemistry (2005)
The aim of this thesis is to synthesize enantiomerically enriched cyclopentenoid and cyclohexenoid type of compounds with quaternary carbon stereocenters that are the simplest precursors of the complex natural products. The first part of the study involves the preparation of ?'-acetoxy ?'-substituted ?,β-unsaturated cyclic ketones. Methylation, ethylation, benzylation and allylation of cyclohexenone and cyclopentenone derivatives are performed. Then, these compounds are regioselectively oxidized at the ?'-p...
Synthesis of novel chiral N,N-dialkyl substituted 1,4-amino alcohols and applications in asymmetric transformation reactions
Çakır, Esen; Tanyeli, Cihangir; Department of Chemistry (2007)
Amino alcohols are valuable bioactive substances and frequently used as chiral catalyst in various asymmetric transformation reactions. In the synthetic route, the asymmetric synthesis of novel chiral N,N-dialkyl substituted chiral 1,4-amino alcohols are performed starting with meso-anhydride 38. Quinine-mediated desymmetrization of the anhydride with methanol afforded (2S,3R)-cis-monoester 39 with a high enantiomeric excess (up to 98% ee). Chemoselective amidation of hemiester with various N,N-dialkyl subs...
Synthesis of heterocyclic amine substituted novel 1,4-Aminoalcohols and applications in various asymmetric transformations
Keskin, Eda; Tanyeli, Cihangir; Department of Chemistry (2007)
Aminoalcohols are very important compounds used in various asymmetric transformations as chiral ligands or chiral auxiliaries. In this thesis, four novel heterocyclic amine substituted chiral 1,4-aminoalcohols were synthesized. In the synthetic strategy, amide esters were synthesized from (2S, 3R)-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene-2-carboxylic acid by DCC coupling method. Subsequent reduction of these amide esters lead to target 1,4-aminoalcohols. The activities of these novel chiral 1,4-aminoalcoho...
Synthesis of various camphor-based chiral pyridine derivatives
Işık, Murat; Tanyeli, Cihangir; Department of Chemistry (2005)
Chiral aromatic nitrogen heterocycles are finding many applications in asymmetric organic synthesis, particularly as ligands in the preparation of chiral metal complexes. Since camphor-based chiral auxiliaries are known to be especially effective, a number of pyridines fused to the camphor skeleton have been reported. It is well known that nicotinic acid and its derivatives exhibiting qualitatively the biological activity of nicotinamide, which acts as an electron acceptor in many biological redox reactions...
Citation Formats
IEEE
ACM
APA
CHICAGO
MLA
BibTeX
C. Açıkgöz, “Synthesis of ferrocenyl cycloheptadienones,” M.S. - Master of Science, Middle East Technical University, 2005.