Studies on Photocleavage Reaction of Arylmethyl and Diarylmethyl Carboxylates

芳甲基和二芳基甲基羧酸盐光裂解反应的研究

• 批准号: 05453037
• 负责人: IWAMURA Michiko
• 金额: $ 3.2万
• 依托单位: Toho University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453037/
• 关键词: Diarylmethyl Esters; Photocleavage Reaction; Diarylmethyl Radicals; Oxygen trapping; Protecting Groups; Caged Groups; Caged-cAMP; Photo-induced Electron Transfer; カルボン酸エステル; 1-ピレニルメチル基; 2-ナフチルメチル基; 酸素付加

1. Photolysis under Ar of diarylmethyl carboxylates, except for aromatic carboxylates, generally gives a diaryl ketone and a diarylmethanol Diarymethyl radicals formed by homolytic cleavage of C-0CO bond (beta-cleavage) quite efficiently trap trace amount of oxygen present in the reaction media under Ar to give the ketone and alcohol. At the same time, the reaction of oxygen with the alkyl radical derived from decarboxylation of the acyloxy radical gives an aldehyde or ketone. Cleavage of O-CO bond (alpha-cleavage) is concluded not to take place. High efficiency of oxygen trapping by diarylmethyl radicals is related to their stability and bulkiness by the product studies of photolysis of several diarylmethyl carboxylates. alpha- (1-Naphthyl) benzyl and 3,4-benzofluorenyl radicals are above all most efficiently trap oxygen.2. Application of this oxygen trapping reaction to the synthesis of an aldehyde from a carboxylic acid has not been successful.3. Fluorescence quenching exciplex formation in 2- (1-pyrenyl) ethyl p-cyanobnzoate was studied in detail, especially the effect of solvent polarity has been studied systematically for the first time.4. Efficient and convenient procedure for the protection of amino and phosphate groups has established. Various kinds of protected amino acids, peptides and phosphates are made by this procedure and their deprotection by irradiation was examined. (1-Pyrenyl) methyl was found not to be good for biological application because it decreases the solubility in water. More water soluble cinnnamoyl and 4-chmarinylmethyl are introduced to Leu-Leu-OMe and cAMP as caged groups and their in vitro photolytic behavier was studied.

1. 二芳基甲基羧酸盐在Ar下光解，除芳香羧酸盐外，一般生成二芳基酮和二芳基甲醇。二芳基甲基自由基通过C-0CO键的均裂裂解（β -裂解）形成，能有效地捕获反应介质中存在的微量氧，生成酮和醇。同时，氧与乙基自由基脱羧生成的烷基自由基反应生成醛或酮。O-CO键的解理（α -解理）不会发生。对几种二芳基甲基羧酸盐光解产物的研究表明，二芳基甲基自由基的高捕氧效率与它们的稳定性和体积有关。-（1-萘基）苄基和3,4-苯并芴基自由基首先最有效地捕获氧。这种捕氧反应在由羧酸合成醛中的应用还没有成功。详细研究了2-（1-芘基）对氰酸乙酯荧光猝灭异构体的形成，特别是首次系统地研究了溶剂极性对荧光猝灭异构体的影响。建立了保护氨基和磷酸基团的高效、便捷的程序。用该方法制备了各种受保护的氨基酸、多肽和磷酸盐，并对其辐照脱保护进行了研究。（1-芘基）甲基降低了其在水中的溶解度，不利于生物应用。在Leu-Leu-OMe和cAMP中引入更多的水溶性肉桂酰和4-chmarinylmethyl，研究了它们的体外光解行为。

项目成果

Kawakami,J.: "Intramolecular Fluorescence Quenching and Exciplex Formation in ω-(1-Pyrenyl)alkyl p-Cyanobenzoates." J.Phys.Org.Chem.7. 31-42 (1994)

Kawakami, J.：“ω-(1-芘基)烷基对氰基苯甲酸酯中的分子内荧光猝灭和激基复合物形成。”J.Phys.Org.Chem.7 (1994)。

Furuta,T.: "Stereodivergent Synthesis of Two Diastereoisomeric Enoates by Asymmetric Horner-Wadsworth-Emmons Reaction using a Single Chiral Auxiliary." J.Chem.Soc.,Chem.Commun.2167-2168 (1994)

Furuta,T.：“使用单一手性辅助剂通过不对称霍纳-沃兹沃斯-埃蒙斯反应合成两种非对映异构体烯酸酯。”

Furuta,T.: "A Direct Esterification of Phosphates with Various Halides and Its Application to a Synthesis of cAMP alkyl triester." J.Chem.Soc.,Perkin Trans.I. 24. 3139-3142 (1993)

Furuta,T.：“磷酸盐与各种卤化物的直接酯化及其在 cAMP 烷基三酯合成中的应用。”

Furuta, T., Torigai, H., Osawa, T.and Iwamura, M.: "A Direct Esterification of Phosphates with Various Halides and Its Application to a Synthesis of cAMP alkyl triester." J.Chem.Soc., Perkin Trans. I24. 3139-3142 (1993)

Furuta, T.、Torigai, H.、Osawa, T. 和 Iwamura, M.：“磷酸盐与各种卤化物的直接酯化及其在 cAMP 烷基三酯合成中的应用”。

Okada, S., Yamashita, S., Furuta, T.and Iwamura, M.: "(1-Pyrenyl) methyl Carbamates for Fluorescent 'Caged' Amino Acids and Peptides." Photochem. and Photobiol.(in press). (1995)

Okada, S.、Yamashita, S.、Furuta, T. 和 Iwamura, M.：“用于荧光‘笼状’氨基酸和肽的(1-芘基)甲基氨基甲酸酯。”