• Journal of the Korean Chemical Society
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• v.42 no.2
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• pp.177-183
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• 1998

By the reactions of a $C_{2}$-chiral ligand, (+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene(6) with $[\pi-allyl chloroplatinum(II)]_4$, and $CpCo(CO)_2$ respectively, three new complexes, ($\pi$-allyl)platinum(II)(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene perchlorate(1), ($\pi$-allyl)platinum(II)(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene chloride(2), ($\eta^5$-cyclopentadienyl)cobalt(I)-(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene(3) were prepared. $\eta^3$-Cyclohexenyl)palladium(II)1,2-bis(diphenylphosphino)ethane perchlorate(4) was obtained by the reaction of ($\eta^3$-cyclohexenyl)palladium(II) chloride dimer with a symmetric ligand, 1,2-bis(diphenylphosphino)ethane and lithium perchlorate. These complexes were identified by NMR-, IR-, and Mass-Spectrophotometers and elemental analyzer.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.1929-1930
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• 2007

• Journal of the Korean Chemical Society
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• v.30 no.6
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• pp.516-520
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• 1986

This study is related to reactivity of dioxygen bridged palladium complexes having ${\pi}$-allyl ligands. In this case, new dioxygen bridged palladium complexes were prepared using superoxide ion$(O_2^-)$ as an oxygen source. Reactions of the dioxygen palladium complexes prepared in the study were examined in order to clarify the nature of the coordinated dioxygen. Treatments of a solution of the dioxygen bridged palladium complexes in benzene by water, methanol and acetic acid gave hydrogen peroxide $(H_2O_2)$ as hydroxy-, methoxy-, and acetoxybridged palladium complexes, respectively. The dioxygen bridged palladium complexes reacted also with substitution phenols of salicylaldehyde, 8-hydroxyquinoline and active methylenes of acetylacetone, dimethyl malonate to afford mononuclear complexes of palladium and hydrogen peroxide. The results suggest that dioxygen is coordinated as peroxo $(O_2^{2-})$ in the complexes and behaves as a strong base.

• Journal of the Korean Chemical Society
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• v.27 no.6
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• pp.441-448
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• 1983

A wide variety of vinylic bromides such as (Z)-1-bromopropene, 1-bromo-2-methylpropene, 2-bromo-3-methyl-2-butene, (E)-ethyl 2-methyl-3-bromo-2-propenoate, 1-bromo-cyclohexene has been found to react with ethyl acrylate, ethyl 3-butenoate, allyl cyanide, (E)-ethyl crotonate, ethyl 4-pentenoate, methyl 10-undecenoate and methyl methacrylate in the presence of triethylamine and a palladium acetate-triorthotolylphosphine catalyst. In general, 2,4-dienoic acid derivatives were obtained in good yield and stereochemistry of the products was determined. Using this method, four, five and eleven carbon-carbon extension with ethyl 3-butenoate, ethyl 4-pentenoate and methyl 10-undecenoate was also possible.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.636-646
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• 2009

A series of the noble palladium complexes containing $\beta$-ketoiminate ligands with internal bases, [Pd(${\eta}^3$-allyl)($\beta$- ketoiminate)], [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] and [Pd(Me)($\beta$-ketoiminate)], have been successfully prepared. Crystallographically determined structures showed that these complexes are distorted square planar and pendant bases of the $\beta$-ketoiminate ligands fail to coordinate to the metal in the first two classes of complexes while bases do coordinate in the 3rd class complexes. These complexes are active towards norbornene polymerization on activation with $H(OEt_2)_2BAr^'_4$ (Ar' = 3,5-bistrifluoromethylphenyl) and modified methylalumioxane (MMAO). MMAO is more efficient for the activation for polymerization. Generally, the polymerization activity increases with the following order; [Pd(allyl)($\beta$-ketoiminate)] < [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] < [Pd(Me)($\beta$-ketoiminate)].

• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.157-160
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• 2005

Allylindium and propargylindium reagents in situ generated from the reactions of indium with allyl halides and propargyl halides could participate as nucleophiles in Pd-catalyzed substitution reactions of allyl carbonates to produce 1,5-dienes and 1,5-enynes in good yields. $\beta$-Hydride elimination products were produced in case of carbonates having $\beta$-hydrogens. Because organoindium reagents obtained from allyl or propargyl halides and indium have previously not been used to Pd-catalyzed allylic and propargylic substitution reactions, these results should provide more opportunities for the development of new C-C bond forming reactions.

• Polymer(Korea)
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• v.27 no.5
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• pp.429-435
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• 2003

Vinyl addition copolymerizations of norbornene (NB) and 5-vinyl-2-norbomene (VNB) were carried out using a cationic η$^3$-allyl palladium catalyst in the various mole ratio of comonomers. The copolymers could be obtained in good yield (65∼85%) with high weight-average molecular weights (M$_{w}$ > 760,000). Depending on increasing VNB contents, the molecular weight and yield of the copolymers decreased. FT-IR analysis confirmed that actual contents of VNB in polymer were proportional to the feeding content of VNB. From $^1$H-NMR spectroscopy, we found that both exo and endo VNB isomer were copolymerized with NB. Thermal stabilities of NB-VNB copolymers were independent on the VNB content and their initial decomposition temperatures were about 300 C. The NB-VNB copolymers were followed by epoxidation by using m-CPBA and hydroxylation by 9-BBN, respectively, and these post-polymers were characterized by FT-IR spectroscopy and $^1$H-NMR analysis..

• Polymer(Korea)
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• v.28 no.3
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• pp.245-252
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• 2004

We synthesized the vinyl addition-type polynorbomene copolymers using two monomers [5-hexyl-2-norbornene (HNB) and 5-methyleste-2-norbornene(MES-NB)] by means of a cationic ${\eta}^3$-allyl palladium catalyst system{[(${\eta}^3$-allyl)palladium(tricyclohexylphosphine) trifluoroacetate] and [lithium tetrakis(pentafluorophenyl) borate ${\cdot}$2.5 etherate]}. The molecular weights and yields of copolynorbomenes polymerized in various conditions were measured to investigate an optimum polymerization conditions to obtain highly ester-functionalized polynorbomenes. As a Pd catalyst content increased, the molecular weights (Mw) of polymers decreased while polymer yields increased. Also, as a Li cocatalyst content increased, the Mw’s and yields of polymers increased at the same time. The Mw’s of copolymers were also controlled by chain transfer agents such as 1-hexone, 1-octene and 1-decene, and we found that longer 1-decene and 1-octene were more efficient to reduce the Mw’s of polynorbornenes than 1-hexene. On the other hand, the content of chain transfer agents did not give influence significantly on polymer yields. From the $^1$H-NMR and GPC analysis of HNB/MES-NB(feed ratio of 40/60 mol%) copolymer, we found that this copolymer had an about 25 mol% of ester portion and a high molecular weight of 270,000.

• YAKHAK HOEJI
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• v.34 no.3
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• pp.166-170
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• 1990

An efficient synthetic route to macrolide is described. Eight-membered lactone was synthesized via palladium catalyzed intramolecular alkylation of allylic carbonate in high yield.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1727-1728
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• 2006