In the first part of this thesis, it is aimed to develope methods for the synthesis of trisubstituted
pyrrrole derivatives. 2-Aminopyrrroles, alkoxy and sulfonyl substittitued
pyrrole derivatives as well as pirolinones show interesting biological activities and
are precursor of well know drugs. Although there is a number of methods for the
synthesis of pyrroles, the synthesis of 2-aminopyrroles is limited to few works and is
not widely known. Therefore, it is still an important goal in organic chemistry to
improve methods for the synthesis of multifunctionalized pyrrole derivatives and
pyrrolinones.
Alkylation of & / #946 / -dicarbonyl compounds with bromoacetonitrile furnishes & / #945 / -
cyanomethyl-& / #946 / -dicarbonyl compounds. The condensation reaction of & / #945 / -
v
cyanomethyl-& / #946 / -dicarbonyl compounds with amines catalyzed by p-TsOH affords the
corresponding enamines and further base catalyzed cyclization furnishes 2-
aminopyrroles in high yields, moreover, zinc perchlorate-catalyzed addition of
amines, alcohols and thiols to the nitrile carbon of & / #945 / -cyanomethyl-& / #946 / -ketoesters
followed by annulation gives the 5-alkoxy and 5-alkylsulfanylpyrrole-3-carboxylates
in high yields.
In the second part of the thesis, reactions of a broad range of acyl phosphonates with
& / #945 / -bromo acetophenones at room temperature in the presence of different bases were
described to afford two diastereomeric epoxy phosphonates in good yields and high
diastereoselectivities. The diastereoselectivity of this reaction is easily controlled by
changing the base. Accordingly, changing the base from Cs2CO3 to DBU changes the
diatereomeric ratio (trans/cis) from 5/3 to 9/1. Furthermore, the treatment of trans
isomer with DBU shows a complete conversion to the corresponding cis isomer.
Additionally, these highly functionalized epoxyphosphonates are shown to be useful
intermediates to give several reactions
| Identifer | oai:union.ndltd.org:METU/oai:etd.lib.metu.edu.tr:http://etd.lib.metu.edu.tr/upload/3/12610338/index.pdf |
| Date | 01 January 2009 |
| Creators | Emrullahoglu, Mustafa |
| Contributors | Demir, Ayhan Sitki |
| Publisher | METU |
| Source Sets | Middle East Technical Univ. |
| Language | English |
| Detected Language | English |
| Type | Ph.D. Thesis |
| Format | text/pdf |
| Rights | To liberate the content for public access |
Page generated in 0.0023 seconds