• Journal of Photoscience
• /
• 제12권2호
• /
• pp.63-66
• /
• 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
• /
• 제12권3호
• /
• pp.155-162
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• 제26권5호
• /
• pp.717-718
• /
• 2005

• 대한화학회지
• /
• 제53권3호
• /
• pp.302-307
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• 제33권8호
• /
• pp.2703-2706
• /
• 2012

New C60 fullerenes derivatives [G1]-C60 (1) and [G2]-C60 (2) comprising of phenylenevinylene bridges and phenylquinoline peripheral surface groups were synthesized by 1,3-dipolar cycloaddition reaction of fullerene C60 with azomethine ylide in situ generated from [Gx]-CHO dendrons (x = 1 and 2) and sarcosine.

• Bulletin of the Korean Chemical Society
• /
• 제31권9호
• /
• pp.2453-2458
• /
• 2010

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.