Synthesis Of Ferrocenyl Cycloheptadienones

Description

SYNTHESIS OF FERROCENYL CYCLOHEPTADIENONES


A&ccedil / ikg&ouml / z, Canet
M.S., Department of Chemistry
Supervisor: Assoc. Prof. Dr. Metin Zora

August 2005, 85 pages


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, ferrocenyl&not / propyne (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, &amp / #61537 / -hydroxycycloheptadienones 28 and cyclobutenones 29, depending on the substitution pattern of the alkyne moiety. Interestingly, &amp / #61537 / -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.

Links & Downloads

1. http://etd.lib.metu.edu.tr/upload/3/12606365/index.pdf

Tags

QD Organic Chemistry 241-441

tz reaction.

Additional Fields

Identifer	oai:union.ndltd.org:METU/oai:etd.lib.metu.edu.tr:http://etd.lib.metu.edu.tr/upload/3/12606365/index.pdf
Date	01 August 2005
Creators	Acikgoz, Canet
Contributors	Zora, Metin
Publisher	METU
Source Sets	Middle East Technical Univ.
Language	English
Detected Language	English
Type	M.S. Thesis
Format	text/pdf
Rights	To liberate the content for public access