4th EucheMs chemistry congress

Poster Session 1
s1067
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - organic chemistry
P - 0 4 1 1
PrePArAtion of PoLyCArBonAte with
AnthrACene And Azido PendAnt GrouPS And
itS GrAftinG viA CLiCK CheMiStry
P. S. oMurtAG 1 , A. dAG 1 , h. durMAz 1 , u. S. GunAy 1 ,
G. hizAL 1 , u. tunCA 1
1 Istanbul Technical University, Chemistry, Istanbul, Turkey
This study deals with the synthesis of anthracene- and azidefunctional
cyclic carbonate monomers, anthracen-9-ylmethyl
5-methyl-2-oxo-1,3-dioxane-5-carboxylate and 2-azidoethyl
5-methyl-2-oxo-1,3-dioxane-5-carboxylate, by the reaction
of anthracen-9-ylmethyl 3-hydroxy-2-(hydroxymethyl)-2methylpropanoate
and 2-azidoethyl 3-hydroxy-2-
-(hydroxymethyl)-2-methylpropanoate with ethyl chloroformate
in tetrahydrofuran at room temperature, respectively [1] . The
copolymerization of these anthracene- and azide-functional cyclic
carbonate monomers was carried out successfully via
ring-opening polymerization (ROP) using benzyl alcohol as
initiator, 1,8-diazabicyclo[5.4.0]undec-7-ene and
1-(3,5-bis(trifluorometh1-(3,5-bis(trifluoromethyl))-3-cyclohexyl-
-2-thiourea, as catalyst system [2] . In addition, side chains were
synthesized via atom transfer radical polymerization and ROP.
The grafting reaction of these side chains with the anthraceneand
azide- functional polycarbonate as a main chain was
accomplished under facile conditions via click reactions (CuAAC
and Diels-Alder).
The composition and molecular weight of the
polycarbonates were characterized by 1H NMR and GPC.
Thermogravimetric analysis and differential scanning calorimetry
measurements were used to investigate the thermal properties of
the resulting polymers.
references:
1. Zhang X, Zhong Z, Zhuo R, Macromolecules, 44:
1755–1759, 2011.
2. Sanders DP, Fukushima K, Coady DJ, Nelson A,
Fujiwara M, Yasumoto M, Hedrick LJ, J. Am. Chem. Soc.,
132: 14724–14726, 2010.
Keywords: Polymers; Polymerization;
4 th EucheMs chemistry congress
P - 0 4 1 2
AryLSuLfinAteS AS rePLACeMent of
orGAnoMetALLiC reAGentS in
PALLAdiuM-CAtALyzed CouPLinG reACtionS
d. ortGieS 1 , A. BArtheLMe 1 , S. ALy 1 , P. forGione 1,
B. deShArnAiS 1 , M. de CiCCo 1 , S. rioux 1 , f. Chen 1 ,
1 Concordia University, Chemistry and Biochemistry, Montréal
(Québec), Canada
Substituted biaryls are an important motif in a variety of
pharmacophores, pesticides and chiral ligands. Palladium-catalyzed
cross-coupling reactions employing stoichiometric amounts of
organometallic reagents as nucleophiles are generally utilized for
their synthesis. Therefore multi-step, expensive, moisture-sensitive
and potentially toxic transformations are often needed to access
these coupling partners. Decarboxylative cross-couplings have
recently emerged as an alternative method to overcome these
limitations. We successfully advanced this principle to the use of
aromatic sulfinates salts as analogues of benzoic acids. Our efforts
involving this desulfinylative coupling of substituted
benzenesulfinates with aryl-bromides also led to the development
of a catalytic homo-coupling of aryl-sulfinates under oxidative
conditions. The scope of these reactions will be presented.
Furthermore, their reactivity in aqueous media as a way to develop
a more environmentally benign reaction will be highlighted.
Keywords: Palladium; C-C coupling; Green chemistry; Sulfur;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc