Molecular Recognition of Reactive Species : Asymmetric Photoamination

反应性物质的分子识别：不对称光胺化

• 批准号: 10650837
• 负责人: YASUDA Masahide
• 金额: $ 2.18万
• 依托单位: Miyazaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650837/
• 关键词: Benzocycloalkenes; Photoamination; Diakoxybinaphthols; Asynmetric recognization; Chiral π donors; Benzylidene tartrate; アミノ化反応; アリールシクロプロパン; ベンゾシクロアルケン; ベンゾシクロヘプテン; ベンジリデン酒石鹸エステル; ジベンゾ[a,d]シクロヘブテンイミン

(1) Redox-Photosensitization : In order to perform the photoamination of the substrates such as benzocycloalkenes, arylcyclopropanes, and quadricyclane that has no or weak absorption at near-ultraviolet regions, we applied the photosensitization using biphenyl derivatives and 2, 2-dialkoxy-1, 1'-naphthalene as the redox-photosensitizer. As the results, the photoamination of the substrates proceeded efficiently without the cosumption of the sensitizer.(2) Photoamination in the presence of chiral π-donors : In order to attempt the asymmetric photoamination, the photoamination in the presence of chiral π-donors have been performed. When chiral benzyl menthyl ethers were used, the specific rotatory of the aminated products depended on the reaction temperature and the chiral π-donors used.(3) Intercalation of chiral π-donors into β-cyclodextrins : Fluorescence spectral changes of (-)-and (+)-dialkyl 2-aryl-1, 3-dioxolane-4, 5-dicarboxylates having the methoxyphenyl group and the rigid conformation by the addition of b-cyclodextrin were investigated. In some cases, the enhancing effects on the fluorescence were different in (+)-and (-)-isomeres.

(1)氧化还原-光敏化：为了实现苯并环烯烃、芳基环丙烷和四环烷等在近紫外区无吸收或吸收较弱的底物的光胺化，我们采用联苯衍生物和2，2-二烷氧基-1，1 '-萘作为氧化还原光敏剂进行光敏化。结果表明，在不消耗敏化剂的情况下，底物的光胺化反应有效地进行。(2)在手性π-给体存在下的光胺化：为了尝试不对称光胺化，已经进行了在手性π-给体存在下的光胺化。当使用手性苄基薄荷醚时，胺化产物的比旋光度取决于反应温度和所用的手性π-给体。(3)手性π-给体在β-环糊精中的嵌入：研究了具有刚性构象的2-芳基-1，3-二氧戊环-4，5-二羧酸（-）-和（+）-二烷基酯与β-环糊精加成后的荧光光谱变化。在某些情况下，（+）-和（-）-异构体对荧光的增强作用是不同的。

项目成果

M.Yasuda: "Solvent Parameter based on the exciplex emission of(2-naphthoxy)polyoxalkyl p-cyanobenzoate" J.Photochem.Photobiol.A.Chem.in press. (1999)

M.Yasuda：“基于(2-萘氧基)聚氧烷基对氰基苯甲酸酯的激基复合物发射的溶剂参数”J.Photochem.Photobiol.A.Chem.in press。

M. Yasuda: "Photoamination of 1,2-diarylcyclopropanes Using 2,2'-Dialkoxy-1,1'-binaphthalene as Redox-Photosensitizer"Chem. Lett.. 12号. 1269-1270 (1999)

M. Yasuda：“使用 2,2-二烷氧基-1,1-联萘作为氧化还原光敏剂对 1,2-二芳基环丙烷进行光胺化”Chem. Lett. No. 12. 1269-1270 (1999)

M.Yasuda: "Photoamination of Alkenylnaphthalene with Ammonia via Electron Transfer" Bull.Chem.Soc.Jpn.71巻、7号. 1655-1660 (1998)

M.Yasuda：“通过电子转移对烯基萘与氨进行光氨化”Bull.Chem.Soc.Jpn.Volume 71，Issue 7. 1655-1660 (1998)

M.Yasuda: "Photoamination of Alkenylnaphthalenes with Ammonia via Electron Transfer"Bull.Chem.Soc.Jpn. 71. 1655-1660 (1998)

M.Yasuda：“通过电子转移用氨光氨化烯基萘”Bull.Chem.Soc.Jpn。

M.Yasuda: "Solvent Parameter Based on the Exciplex Emission of (2-Naphthoxy) polyalkyl p-Cyanobenzoates"J.Photochmem.Photobiol.A : Chemistry. 121. 149-155 (1999)

M.Yasuda：“基于（2-萘氧基）聚烷基对氰基苯甲酸酯的激基复合物发射的溶剂参数”J.Photochmem.Photobiol.A：化学。