• Bulletin of the Korean Chemical Society
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• 제26권9호
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• pp.1339-1343
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• 2005

The N-inversion energies and nucleophilic ring-opening reactions of N-substituted aziridine compounds are investigated using B3LYP/6-31+$G^*$ methods, where substituents (R) on the nitrogen atom has been H (1), Me (2), Ph (3), Bn (4), CHMePh (5), $CO_2Me$ (6), COPh (7) and $SO_2Ph$ (8). The N-inversion energy with X group are decreased as the following order: R = CHMePh (17.06 kcal/mol) $\gt$ Me (16.97) $\gt$ Bn (16.70) $\gt$ H (16.64) $\gt$ $SO_2Ph$ (12.18) $\gt$ Ph (8.91) $\gt$ COPh (5.75) $\gt$ $CO_2Me$ (5.48). For reactivity of the ring opening toward cyanide ion, the aziridine 6 (R=$CO_2Me$) is shown to be the most reactive one. During the ring opening of aziridine 6 by CN$^{\ominus}$, the torsional OCNC angle becomes near to $180^{\circ}$, where the geometry allows for the effective incorporation of electrons of the nitrogen atom to the C=O bond. It would be a possible driving force for nucleophilic ring opening reaction as well as decreasing the N-inversion energy barrier. Regarding to the regioselectivity, the orientation of nucleophile in ring opening reaction appears to be different in the case of 9 and 10. The results are discussed in terms of steric/electronic effect of the $C_2$-substituents.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.3075-3078
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• 2009

• Bulletin of the Korean Chemical Society
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• 제27권3호
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• pp.345-354
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• 2006

Ionic liquids are alternative reaction media of increasing interest and are regarded as an eco-friendly alternatives, of potential use in place of the volatile organic solvents typically used in current chemical processing methods. They are emerging as the smart and excellent solvents, which are made of positive and negative ions that they are liquids near room temperature. The nucleophilic substitution reaction is one of the important method for inserting functional groups into a carbon skeleton. Many nucleophilic substitution reactions have been found with enhanced reactivity and selectivity in ionic liquid. In this review, some recent interesting results of nucleophilic substitution reactions such as hydroxylations, ether cleavages, carbon-X (X= carbon, oxygen, nitrogen, fluorine) bond forming reactions, and ring opening of epoxides in ionic liquids are discussed.

• Bulletin of the Korean Chemical Society
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• 제26권5호
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• pp.829-832
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• 2005

• Bulletin of the Korean Chemical Society
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• 제30권1호
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• pp.163-171
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• 2009

Few $\alpha$-Hydroxy-$\beta$-amino acids were synthesized via various nucleophilic addition of the epoxide and followed by stereoselective nucleophilic substitution reaction and eliminative cleavage of the acetal selectively in diacetal compound. One of the synthesized $\alpha$-Hydroxy-$\beta$-amino acid reacted with L-leucine methylester to give corresponding dipeptide in good yields.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1531-1534
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• 2009

(2S,3R)-3-Hydroxy-2-(hydroxymethyl)-3,6-dihydro-2H-pyridine 8, an important precursor for the synthesis of polyhydroxylated piperidine azasugars, has been prepared from L-serine. Highly stereoselective nucleophilic addition to amino aldehyde 5 gave the corresponding allylic alcohol 6 which proceeded to give dihydro-2H-piridine 7a via a Grubbs II catalyzed RCM. Stereoselective H-bond directed epoxidation of allylic alcohol led to the oxiranyl alcohol 9 which was easily converted to L-deoxyaltronojirimycin by regioselective ring opening.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2153-2161
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• 2007

The transition metal-induced in situ generation of carbene complexes from alkynes having a carbonyl or imino group as a nucleophilic functionality has been investigated. These reactive carbenoid species are generated with high atom efficiency through a 6-endo-dig cyclization mode based on the electrocyclization of vinylidene complexes or a 5-exo-dig cyclization mode in π-alkyne complexes, and have been found to serve as versatile intermediates in catalytic carbene transfer reactions. Highlighted and reviewed in this account are the generation and preparation of pyranylidene, furylcarbene, pyrrolylcarbene, and vinylcarbene complexes and their application to [3,3]sigmatropic rearrangement of acylcyclopropylvinylidenes, catalytic cyclopropanation reactions, [2,3]sigmatropic rearrangement or condensation reactions via ylides, ring-opening and substitution reactions with heteroaromatic compounds, and catalytic isomerization of oligoynes.

• 약학회지
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• 제40권3호
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• pp.300-305
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• 1996

The base-induced elimination of N-protected 2-(bromomethyl)pyrrolidines 12a-c with KHMDS in THF at -78$^{\circ}C$ for 1h gave exocyclic enamines 13a-c. The acidic catalyzed pr otonation on ${\beta}$-carbon atom of 2-(methylene)pyrrolidines 13a-c with $H_3PO_4$ formed endocyclic N-iminium intermediates 14(or 15). Nucleophilic attack of alpha-carbon atom and hydrolysis of N-iminium ion gave carbocationic adduct (aminoalcohol) 16 from which 5-amino-2-pentanones 17a-c were formed after deprotonation.

• 대한화학회지
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• 제20권4호
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• pp.295-298
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• 1976

Organothioenamine phosphonate와 styrene oxide 와의 반응에서 얻어진 생성물의 구조를 규명한 결과 그것이 cyclopropane 유도체임을 알았다. 이것은 반응이 styrene oxide에 대한 thioenamine phosphonate의 친핵공격에 의해서 생긴 산소 음이온이 다시 인 원자를 공격함으로서 중간체로 betain이 형성 된다음 이어서 약한 P-C 결합이 끊어지면서 생성물로 이끌어져 감을 가리켜 주고있다. 또한 생성물의 광학활성을 조사한 결과는 우회전성 이어서 이 반응은 중간체에서 생긴 benzyl carbon의 입체적 효과를 받으며 어디까지나 안정한 경로를 거쳐서 이끌어져 감을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.1981-1984
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• 2006

Novel amphiphilic, thermo-responsive polyaspartamides which showed both LCST (lower critical solution temperature), and sol-gel transition were prepared and characterized. The polyaspartamide derivatives were synthesized from polysuccinimide, the polycondensate of aspartic acid monomer, via successive nucleophilic ring-opening reaction by using dodecylamine and N-isopropylethylenediamine (NIPEDA). At the intermediate composition ranges, the dilute aqueous solution exhibited a thermally responsive phase separation due to the presence of LCST. The phase transition temperature was controllable by changing the content of pendent groups. In addition, a physical gelation, i.e. the sol-gel transition was observed from the concentrated solutions, which was elucidated by dynamic viscoelastic measurements. These novel injectable and thermo-responsive hydrogels have potential for various biomedical applications such as tissue engineering and current drug delivery system.