Chemistry of the Hypermodified Base from Mammalian Phenylalanine Transfer Ribonucleic Acids

哺乳动物苯丙氨酸转移核糖核酸超修饰碱基的化学

• 批准号: 61570998
• 负责人: ITAYA Taisuke
• 金额: $ 1.54万
• 依托单位: Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-61570998/
• 关键词: Hypermodified fluorescent base; Condensed tricyclic nucleic base; Wittig reaction; Heck reaction; Chiral synthesis; Optically active <beta>,<gamma>-unsaturated amino acid; Cyclic diester of Carbonic acid; 選択的脱オキシ化反応; 微量蛍光塩基; 超修飾塩基; 絶対配置; 環状炭酸ジエ

1. The synthesis of a model compound for the title fluorescent base has been established by a series of the reactions: the Witting reaction between 1-benzy1-7-(triphenylphosphoniomethyl)wye and isobutyraldehyde, oxidation with OsO_4, cyclic carbonate formation by treatment with (COCL)_2, and catalytic hydrogenolysis over Pd-C.2. The Heck reaction of 1-benzy1-7-iodowye with (S)-N-(methoxycarbonyl)vinylglycine followed by methylation has provided an improved method for the synthesis of'(S)-(E)-1-benzy1-7-[3-methoxycarbonyl-3-(methoxycarbonyl)amino-1-butenyl]wye, the key intermediate for the synthesis of the target compounds. Oxidation of the intermediate with OsO_4 gave a pair of the diastereomers of the diols and the (S,S,S) configurations were assigned to the major product by means of X-ray analysis. According to the model experiments mentioned above, the diols were transformed into [R-(R^*,S^*)]- and [S-(R^*,R^*)]-hydroxywybutine, two alternatives for the title base.3. Investigation of the chemical properties of the isomers of hydroxywybutine and isolation of the base from natural sources are in progress.

1. 通过1-苄基- 1-7-（三苯基膦甲基）烷与异丁醛的Witting反应、OsO_4氧化、（COCL）_2处理生成环状碳酸盐、Pd-C.2催化氢解等一系列反应，建立了该荧光碱的模型化合物的合成。1-苄基1-7-碘啶与(S)- n -（甲氧羰基）乙烯基甘氨酸的Heck反应并甲基化，为合成目标化合物的关键中间体'(S)-(E)-1-苄基1-7-[3-甲氧羰基-3-（甲氧羰基）氨基-1-丁烯基]wye提供了一种改进的方法。中间体与OsO_4氧化得到二醇的一对非对映体，x射线分析表明主要产物为（S，S，S）构型。根据上述模型实验，二醇转化为[R-(R^*,S^*)]-和[S-(R^*,R^*)]-羟基wybuine，这是标题碱的两种替代品。羟基wybutine同分异构体的化学性质的研究和从天然来源中分离碱的研究正在进行中。

项目成果

Taisuke Itaya: "Synthesis of Optically Active Forms of Hydroxy-Y Base, the Minor Component of Rat Liver Phenylalanine Transfer Ribonucleic Acid" Tetrahedron Lett.27. 4043-4046 (1986)

Taisuke Itaya：“羟基-Y 碱的光学活性形式的合成，羟基-Y 碱是大鼠肝脏苯丙氨酸转移核糖核酸的次要成分”四面体 Lett.27。

板谷泰助: 有機合成化学協会誌. 45. (1987)

Taisuke Itaya：有机合成化学学会杂志 45。（1987）

板谷泰助: 有機合成化学協会誌. 45. 431-444 (1987)

Taisuke Itaya：有机合成化学学会杂志 45. 431-444 (1987)。

Taisuke Itaya: Tetrahedron Lett.27. 4043-4046 (1986)

Taisuke Itaya：四面体 Lett.27。

Taisuke Itaya: "The Modified Components of Transfer Ribonucleic Acids" Yuki Gosei Kagaku Kyokai Shi. 45. 431-444 (1987)

Taisuke Itaya：“转移核糖核酸的修饰成分”Yuki Gosei Kagaku Kyokai Shi。