• Bulletin of the Korean Chemical Society
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• v.10 no.2
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• pp.129-132
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• 1989

Reactions of thebaine with phenylsulfonylpropadiene in various solvents were investigated. It was found that Diels-Alder reaction adduct was obtained in nonpolar solvent, while addition reaction adduct was obtained in polar solvent. Transformations of these two products were also carried out.

• Journal of the Korean Chemical Society
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• v.40 no.7
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• pp.483-491
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• 1996

Dieis-Alder reaction between cyclopentadiene and 5-membered ring compounds which have exo-cyclic double bond has been studied using the PM3 method. Transition states do not show large geometrical change with the variation of dienophiles. Two isomers are possible due to the rotation of the exo-cyclic double bond of a dienophile. The reactivity for the formation of different products are explained using the FMO energy gap. The exo and endo selectivity of the reaction has been also studied from the correlation between the deformation energy and the activation barrier. Minimum energy reaction path is discussed using the Curtin-Hammett principle.

• Bulletin of the Korean Chemical Society
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• v.4 no.1
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• pp.41-44
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• 1983

The chlorine addition and Diels-Alder cycloaddition of cyclopentadiene to 1, 4-benzoquinone-4-(O-methyloxime) have been studied MO theoretically. It has been shown that the reactions occur predominantly to the quinone ring double bond which is oriented anti to the nitrogen lone pair due to an n-${\sigma}^*$ interaction between the nitrogen lone pair, n, and the app. vicinal bond, causing the ${\pi}$ bond to be weakened and destabilized due to the less conjugation from reduced delocalization.

• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.533-538
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• 2004

Canonical sampling method has been presented to generate the initial conditions for reactive flux studies of organic reactions in water. Velocity Verlet version of Nose-Hoover chain dynamics algorithm has been employed to sample the initial conditions according to canonical distribution. The unstable normal mode of a transition state has been introduced to define a dividing plane separating reactant and product regions in reaction processes. This method has been implemented and tested for the case iels-Alder reaction of methyl vinyl ketone (MVK) and cyclopentadiene (CPD) in water, providing a reliable tool for further reactive flux molecular dynamics studies in condensed media.

• Bulletin of the Korean Chemical Society
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• v.18 no.7
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• pp.754-760
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• 1997

Through a sequence of reactions including Diels-Alder cycloaddition of a furan diene as the key step, 11-oxatricyclo[6.2.1.01,6]undecyl rings were synthesized from 5-methylfurfural with the goal of developing a synthetic protocol to 11-oxabicyclo[6.2.1]undecyl system. The strategy to incorporate an oxygen atom at C6 carbon of tricyclic 11 or 16 by Baeyer-Villiger oxidation was unsuccessful, implicating that there is too much steric congestion around the carbonyl ketone. As an alternative approach, bicyclic 23 and 24 were prepared from 2-methylfuran via known tricyclic 20. Cyclization of bicyclic 23 and 24 under several reaction conditions also failed to produce hydroxylated product 25 and 26.

• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.340-344
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• 1998

A facile synthesis of 4,5-(1',2'-diphenylethylenedithio)-1,3-dithiole-2-thione (dPhEDT-DTT) is carried out via a Diels-Alder type [2+4] cycloaddition reaction of 1,3-dithiol-2,4,5-trithione oligomer and t-stilbene. Molecular structure of dPhEDT-DTT is determined by x-ray crystallography: space group P1, a=11.694(3) Å, b=12.117(3) Å, c=14.688(3) Å, α=113.12(2)°, β=102.23(2)°, γ=107.02(2)°, V= 1699.1(7) Å3, Z=2. It turns out that dPhEDT-DTT crystallizes as a racemic compound consisting of (R,R) and (S,S) enantiomers. Coupling reaction of dPhEDT-DTO undergone in neat P(OEt)3 yields TTF(SEt)4 instead of ET derivative. When PR3 (R=OEt, OPh, Ph) is used in benzene, toluene or xylene, however, dPhEDT-DTO is decomposed.

• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.491-500
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• 2004

The Lewis acid-catalyzed reactions of anthrone with a variety of ethylenic substrates under various conditions have been studied. It has been observed that depending on kinds of ethylenic substrates and catalysts, products were varied. In particular, the $ZnCl_2$-catalyzed reaction of anthrone with ${\alpha},{\beta}$ -unsaturated ester gave bridged compounds 3 (Diels-Alder adduct type) and mono-Michael adduct 4 exclusively, while the base-catalyzed reaction gave 10,10-bis-Michael adduct as a major product independent of the amount of ethylenic substrate and base. Bridged compounds 3 were easily converted to the corresponding mono-Michael adduct 4 by a catalytic amount of base. Further Michael reaction of mono-Michael adducts with different ethylenic substrates in the presence of a catalytic amount of alkoxide gave unsymmetrical 10,10-bis Michael adducts in good or moderate yields.

• Clean Technology
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• v.29 no.2
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• pp.79-86
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• 2023

The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.

• Biomaterials Research
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• v.22 no.4
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• pp.235-248
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• 2018

Background: Injectable hydrogels have been extensively researched for the use as scaffolds or as carriers of therapeutic agents such as drugs, cells, proteins, and bioactive molecules in the treatment of diseases and cancers and the repair and regeneration of tissues. It is because they have the injectability with minimal invasiveness and usability for irregularly shaped sites, in addition to typical advantages of conventional hydrogels such as biocompatibility, permeability to oxygen and nutrient, properties similar to the characteristics of the native extracellular matrix, and porous structure allowing therapeutic agents to be loaded. Main body: In this article, recent studies of injectable hydrogel systems applicable for therapeutic agent delivery, disease/cancer therapy, and tissue engineering have reviewed in terms of the various factors physically and chemically contributing to sol-gel transition via which gels have been formed. The various factors are as follows: several different non-covalent interactions resulting in physical crosslinking (the electrostatic interactions (e.g., the ionic and hydrogen bonds), hydrophobic interactions, ${\pi}$-interactions, and van der Waals forces), in-situ chemical reactions inducing chemical crosslinking (the Diels Alder click reactions, Michael reactions, Schiff base reactions, or enzyme-or photo-mediated reactions), and external stimuli (temperatures, pHs, lights, electric/magnetic fields, ultrasounds, or biomolecular species (e.g., enzyme)). Finally, their applications with accompanying therapeutic agents and notable properties used were reviewed as well. Conclusion: Injectable hydrogels, of which network morphology and properties could be tuned, have shown to control the load and release of therapeutic agents, consequently producing significant therapeutic efficacy. Accordingly, they are believed to be successful and promising biomaterials as scaffolds and carriers of therapeutic agents for disease and cancer therapy and tissue engineering.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.6 no.1
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• pp.53-58
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• 2020

Pretargeting is a two-component strategy often used for tumor targeting to enhance the tumor-to-background ratio in cancer diagnosis as well as therapy. In the multistep strategy, the highly specific unlabeled monoclonal antibodies (mAbs) with the reactive site is allowed to get localized at tumor site first, and then small and fastclearing radiolabeled chelator with counter reactive site is administered which covalently attaches to mAbs via inverse electron demand Diels-Alder reaction (IEDDA). The catalyst-free IEDDA cycloaddition reaction between 1,2,4,5-tetrazines and strained alkene dienophiles aid with properties like selective bioconjugation, swift and high yielding bioorthogonal reactions are emergent in the development of radiopharmaceutical. Due to its fast pharmacokinetics, the in vivo formed radioimmunoconjugates can be imaged at earlier time points by short-lived radionuclides like ¹⁸F and ⁶⁸Ga; it can also reduce radiation damage to the normal cells. Ultimately, this review elucidates the updated status of pretargeting based on antibodies and IEDDA for tumor diagnosis (PET and SPECT) and therapy.