• Bulletin of the Korean Chemical Society
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• 제25권8호
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• pp.1123-1124
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• 2004

• Bulletin of the Korean Chemical Society
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• 제25권11호
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• pp.1615-1616
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• 2004

• Bulletin of the Korean Chemical Society
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• 제9권3호
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• pp.129-132
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• 1988

The stereochemistry of N-acyliminium cyclizations to form decahydropyrrolo[2,1-a]isoquinolin-3(2H)-ones was studied. Particular attention was paid to the stereocontrol by an acetoxy group present on pyrrolidone ring. Two of the three new chiral centers were formed stereospecifically, and the third was controlled by elimination-hydrogenation sequence.

• Bulletin of the Korean Chemical Society
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• 제8권4호
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• pp.264-269
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• 1987

Various carbocation-mediated cyclizations to tricyclene structure (basically, tricyclo $[2,2,1,0^{2,6}]$ heptane skeleton) were carried out, starting from protonated species of either 3-methyl-2,5-norbornadiene-2-carboxylic acid (10) or 3-methylene-5-norbornene-2-carboxylic acids (18 and 19). The resulting products were individually converted to ${\pi}$-iodotricyclene (35), a pivotal intermediate in almost all syntheses of tricyclene terpenes.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2219-2225
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• 2007

The reaction mechanisms for the cyclizations of N-methyl-2-(2-chloropyridin-3-yloxy)acetamide to 1-methylpyrido[ 3,2-b][1,4]oxazin-2-one and 1-methyl-pyrido[2,3-b][1,4]oxazin-2-one were investigated using ab initio Hartree-Fock, second-order Moller-Plesset perturbation, single point coupled cluster with both single and double substitution, and density functional theory methods. The 5-membered spiro intermediate (2) is optimized from the cyclization of the acyclic reactants through the proton-transfer reaction, and this intermediate proceeds continuously to the 6-membered intermediate through either a stepwise or a concerted reaction. In the stepwise reaction, an N-bridge-type intermediate as a stable structure is optimized, whereas, in the concerted reaction, the O-bridge-type intermediate is not optimized.

• Journal of Photoscience
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• 제7권4호
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• pp.143-148
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• 2000

Studies have been conducted to explore single electron transfer(SET) promoted photocyclization of ($\omega$-phthalimidoalkoxy)acetic acids(alkoxy=ethoxy, n-propoxy and n-butyloxy). Photocyclizations occur in methanol or acetone in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the carboxylic group. These photocyclizations are thought to proceed through pathways involving intramolecular SET from oxygen in the $\alpha$-carboxymethoxy groups to the singlet excited state phthalimide moieties followed by decarboxylation of the intermediate $\alpha$-carboxymethoxy cation fadicals and cyclizations by radical coupling. The photocyclizations occur ca. three times faster in both methanol or acetone with one equivalent of sodium hydroxide added to the reactions and occur slower in acetone than in methanol. The efficient and regiselective cyclization reactions observed for photolyses in methanol represent synthetically useful processes for construction of heterocyclic compounds.

• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.994-1000
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• 2014

Synthesis of tetrahydroimidazo[1,2-a]pyridines and tetrahydropyrido[1,2-a] pyrimidines by a one-pot and three component reaction of ${\alpha}$-oxoketenedithioacetals, diamines and DMAD in water has been described. Different routes for accessing the desired compounds were examined and a few specially designed-substrates have been utilized further to afford the new imidazo and pyrido fused [1,8] naphthyridine tetracyclic compound by $S_NAr$ intramolecular cyclization.

• Bulletin of the Korean Chemical Society
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• 제30권3호
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• pp.599-607
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• 2009

A series of conjugated cyclic and linear enkephalin analogs, Tyr-c[D-A2bu-Gly-Phe-Asp(NH-X)], where X = methyl, stearyl or$ PEG_350$, and Tyr-D-Ala-Gly-Phe-Cys(S-X), where X = methyl, octyl, or farnesyl, were synthesized in solution to investigate the receptor selectivity of opioids based on Schwyzer's membrane compartment $concepts.^{5,6}$ Cyclizations of the target compounds were achieved in high yields (> 60%) employing BOP, $NaHCO_3$ in DMF despite the steric hindrance of the bulky pendant groups. In the binding assay, the hydrophobic fatty acyl conjugates retained $\mu$-receptor selectivity. The unsaturated farnesyl conjugate exhibited the increased binding affinity than the saturated stearyl conjugate for both $\mu$-and $\delta$-opioid receptors. The PEG conjugates displayed the $\delta$-receptor selectivity. The low molecular weight $PEG_350$ conjugate exhibited the increase selectivity than the high molecular weight $PEG_5000$ conjugate to the $\delta$-receptor. The results of this study support the membrane compartment concepts.

• Journal of Photoscience
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• 제10권1호
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• pp.9-20
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• 2003

Recent studies on the photoreactivity of l,4-unsaturated systems have changed some ideas that were firmly established in this area of research for many years. Thus, we have described the first examples of 2-aza-di-$\pi$-methane (2-ADPM) rearrangements promoted by triplet-sensitization and by single electron transfer (SET) using electron-acceptor sensitizers. These reactions afford N-vinylaziridine and cyclopropylimine photoproducts in the first examples of di-$\pi$-methane processes that yield three-membered ring heterocycles. l-Aza-1,4-dienes also undergo SET-promoted l-aza-di-$\pi$-methane (l-ADPM) rearrangements via radical-cation intermediates using electron acceptor sensitizers. In some cases, alternative cyclizations yielding different carbocycles and heterocycles have been observed. The l-ADPM and di-$\pi$-methane (DPM) reactions also occur via radical-anion intermediates on irradiation using electron donor sensitizers. On the other hand, the photoreactivity reported for $\beta$,${\gamma}$-unsaturated aldehydes for many years was decarbonylation to the corresponding alkenes. However, our studies demonstrate that these compounds undergo the oxa-di-$\pi$-methane (ODPM) rearrangement with high chemical and quantum efficiency. A comparison of the photochemical reactivity of $\beta$,${\gamma}$-unsaturated aldehydes and corresponding methyl ketones has shown that the ketones do not undergo the ODPM rearrangement while the corresponding aldehydes are reactive by this pathway. Monosubstituted $\beta$,${\gamma}$-unsaturated aldehydes at C-2 undergo the ODPM rearrangement yielding the corresponding cyclopropane carbaldehydes diastereoselectively. Finally, we have described the first examples of reactions, similar to the well know Norrish Type I process, which take place in the triplet excited state of $\beta$,${\gamma}$-unsaturated carbonyl compounds by excitation of the C-C double bond instead of the carbonyl group.