• Journal of Photoscience
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• 제12권2호
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• pp.63-66
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• 2005

The azomethine ylide forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. N-[(Trimethylsilyl)methyl]-N-mesylbenzamide (5) undergoes the excited state C to O silyl migration reaction to produce azomethine ylide intermediate 13. This ylide undergoes electrocyclization to form transient aziridine intermediate 14 which react further by ring opening to generate N-phenacylamine product 10. On the other hand, photolysis of N-[N-mesyl-N-(trimethylsilyl)methyl]aminoethyl-N-mesylbenzamide (8) brings about desilylation resulting in the production of dimer 17.

• Journal of Photoscience
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• 제10권1호
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• pp.21-35
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• 2003

The photoinitiated intramolecular ylide-olefin addition has been developed as an approach for the construction of one ring and two chiral centers, two rings and three chiral centers or three rings and six chiral centers in a single experimental operation from relatively simple starting materials. These investigations have uncovered several interesting and unusual reactions, which are sensitive to controls such as wavelength, temperature and solvent.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2776-2782
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• 2010

Newly developed Horner-Wadsworth-Emmons (HWE) reagents 5 having triphenylphosphorane ylide subunits readily condensed with various carbonyl compounds under mild reaction conditions to afford $\beta,\gamma$-unsaturated $\alpha$-keto triphenylphorane ylides in good to excellent yields, which were hydrogenated over Pd-C (10%)/$H_2$ (1 atm) to give the corresponding $\alpha$-keto triphenylphorane ylides in quasi-quantitative yields. These triphenyphosphorane ylides have been utilized as the precursors to $\alpha$-keto amide/ester and vicinal tricarbonyl units in Wasserman's synthetic protocols, and have previously been prepared only from carboxylic acids/acid chlorides. Our new approaches provide excellent alternatives for the synthesis of triphenylphosphorane ylide precursors to $\alpha$-keto amide/ester and vicinal tricarbonyl units directly from carbonyl compounds in good to excellent yields.

• Bulletin of the Korean Chemical Society
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• 제32권9호
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• pp.3477-3479
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• 2011

• Bulletin of the Korean Chemical Society
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• 제27권2호
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• pp.319-321
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• 2006

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2051-2055
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• 2007

The solvent effect on sulfur ylide mediated epoxidation reaction was studied systematically. While higher trans/cis ratio of the epoxide was obtained in the more polar solvent, protic solvent produced the lower trans/ cis ratio than any aprotic solvent.

• 대한화학회지
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• 제53권3호
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• pp.302-307
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• 2009

이 연구에서는 N-(트리메틸실릴)메틸프탈이미드의 광화학 반응에서 관찰한 아조메틴 일리드 반응 중간체 생성 과정과 유사하게 N-(트리부틸스탄일)메틸프탈이미드의 광화학반응에서도 생성되는지를 알아보기 위해 N-(트리부틸스탄일)메틸프탈이미드의 광화학반응을 연구하였다. N-(트리부틸스탄일)메틸프탈이미드를 $D_2O-CH_3$CN에서 광화학 반응시킬 때에 생성된 아조메틴 일리드 중간체가 물 분자에 의해 포획되어 생성되는 것으로 예상되는 한 개의 중수소 원자 (D)가 메틸기의 한 개의 수소 (H) 대신에 치환된 $d_1$-N-메틸프탈이미드 생성물을 유일한 생성물로 높은 수율로 생성시킴을 관찰하였다. 이 결과는 이 광화학 반응에서도 매우 효율적으로 들뜬상태 전자전달-스탄일기 이동 과정을 거쳐 트리부틸스탄일 아조메틴 일리드 반응 중간체가 생성되는 것을 뒷받침 해주고 있다. 그러나 이 반응에서 생성된 트리부틸스탄일 일리드 중간체는 스탄일기가 가지는 큰 입체장애 때문에 첨가된 메틸 아크 릴레이트나 아크릴로 니트릴과 같은 친쌍극체 (dipolarophile)에 의해 포획되지 않았다.

• Journal of Photoscience
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• 제12권3호
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• pp.155-162
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• 2005

Results of studies of SET-promoted dipole-forming photochemical group transfer reactions of phthalimide and ${\alpha}-ketoamide$ derivatives are discussed. Azomethine ylide forming photochemical reactions, which are initiated by intramolecular SET from tethered silylmethyl-, carboxymethyl-, and ${\beta}-hydroxyethyl$ containing electron donors to excited states of phthalimides, related maleimides, and conjugated imides, are presented first. Following this, investigations of regioselective 1,4-dipole forming photochemical reactions of N-trialkylsilylmethyl- and N-trialkylstannyl-${\alpha}$-ketoamides are described.

• EDISON SW 활용 경진대회 논문집
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• 제3회(2014년)
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• pp.337-346
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• 2014

Trifluoromethylthiol functional group(이하 -SCF3)은 약학적으로 유용한 물질이다. 이 연구는 최근 개발된 Shibata의 Direct trifluoromethylthiolation reaction의 반응 메커니즘을 계산화학적으로 평가했다. 반응 메커니즘은 크게 Carbene formation, Rearrangement, Electrophilic SCF3 reagent generation 세 단계로 나눌 수 있다. 각 과정에 대해 구조에 대한 full optimization이 진행되었고, 특히 alpha-carbene sulfonyl species의 thermal rearrangement에 관한 첫번째 계산화학적 평가가 이루어졌다.

• Bulletin of the Korean Chemical Society
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• 제34권10호
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• pp.2953-2958
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• 2013

A noble phenylsulfonyl reagent 8 having ${\alpha}$-oxo (cyanomethylene)triphenylphosphorane ylide subunit readily condensed with various alkyl halides under basic conditions to afford ${\beta}$-alkyl-${\alpha}$-oxo-${\beta}$-phenylsulfonyl (cyanomethylene)triphenylphosphorane ylides 9 in excellent yields. These sulfonyl ylides 9 were then reductively desulfonylated with $Na(Hg)/Na_2HPO_4$ in the presence of methanol to provide ${\alpha}$-keto (cyanomethylene)-triphenylphosphorane ylides 2' in good to excellent yields. Our new synthetic approach offers an expeditious access to various ${\alpha}$-keto (cyanomethylene)triphenylphosphorane ylides from alkyl halides utilizing a new phenylsulfonyl reagent as the key reagent under mild reaction conditions in good overall yields.