PREPARATION OF AMINO ACIDS LABELED AT SPECIFIED POSITION FOR LABORATORY USE

制备在指定位置标记的供实验室使用的氨基酸

• 批准号: 59850142
• 负责人: YOSHIKAWA Sadao
• 金额: $ 4.99万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research
• 财政年份: 1984
• 资助国家: 日本
• 起止时间: 1984 至 1985
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-59850142/
• 关键词: Asymmetric Synthesis; Aminoacidato Complex; Amino Alkylmalonato Complex; 部分的重水素化による【^(13)C】シグナルの分裂

On decarboxylation, <(+)_(577)> -(Co(AMM)((4R,6R)-4,6-dimethy1-3,7-diaza-1,9-diaminononane)) <ClO_4> . <H_2O> (1) resulted in 34% R-alaninato and 66% S-alaninato, while <(-)_(546)> -(Co(AMM)((6R,8R)-6,8-dimethy1-2,5,9,12-tetraazatridecane))Br. <3H_2O> (2) resulted in 83% R-alaninato and 17% S-alaninato, where AMM represents an <alpha> -amino- <alpha> -methyl-malonato ion. Two X-ray crystal structure determinations of (1) and (2) have been performed. The results suggest that the important factor which governs the stereoselectivity on decarboxylation, is not the coordination geometry of AMM in the starting complex, but the asymmetric environment around the AMM chelate. The decarboxylation of the AMM complexes using DCl yielded <alpha> -deuterated alaninato complexes.The reaction of <alpha> -aminomalonate (AM) with trans dichloro(3,7-diaza-1,9-nonanediamine)cobalt(III) perchlorate yielded unexpectedly N-(2-aminoethyl)-N-(4-aza6-aminohexyl)( <alpha> , <alpha> -diaminomalonate)cobalt(III) perchlorate. The X-ray crystal structure revealed that the complex has an unusually stable geminal diamine linkage containing an uncoordinated primary amino group, as a result of the new bond formation between the <alpha> -carbon of the <alpha> -aminomalonate unit and one of the secondary nitrogens of the tetraamine ligand.The first obeservation of isotopic multiplets in the <^(13)CNMR> spectra of the cobalt(III) complexes with partially deutrated coordinated <NH_2> or NH groups have been achieved. It has been found that the magnitude of the three bond isotope effect is governed both by the type of the observed carbon atoms and by the dihedral angle C-C-N-H.

在脱羧、<(+)_(577)>——(Co (AMM) ((4 r, 6 r) 4, 6-dimethy1-3, 7-diaza-1, 9-diaminononane)) < ClO_4 >。<(-)_(546)> -(Co（AMM)（(6R,8R)-6,8-二甲基1-2,5,9,12-四氮杂三癸烷））Br。<3H_2O>(2)导致83%的r -丙氨酸ato和17%的s -丙氨酸ato，其中AMM代表< α > -氨基- < α > -甲基丙氨酸ato离子。对(1)和(2)进行了两次x射线晶体结构测定。结果表明，决定脱羧立体选择性的重要因素不是AMM在起始配合物中的配位几何，而是AMM螯合物周围的不对称环境。用DCl对AMM复合物进行脱羧得到< α > -氘化丙氨酸复合物。< α > -氨基丙二酸酯（AM）与反式二氯（3,7-二氮-1,9-壬胺二胺）钴（III）高氯酸盐反应意外生成N-（2-氨基乙基）-N-（4-氮-氨基己基）（< α >, < α > -二氨基丙二酸酯）钴（III）高氯酸盐。x射线晶体结构表明，该配合物具有异常稳定的双胺键，其中含有一个不配位的伯氨基，这是由于< α > -氨基丙酸盐单元的< α > -碳与四胺配体的一个仲氮之间形成了新的键。本文首次在<^(13)CNMR>光谱中观察到钴（III）配合物与部分失氢的<NH_2>或NH基团配合物的多重同位素。已经发现，三键同位素效应的大小与所观察到的碳原子的类型和二面角C-C-N-H有关。

项目成果

J.Am.Chem.Soc.107. (1985)

J.Am.Chem.Soc.107。

J. Am. Chem. Soc.108. (1986)

J. Am.

J.Am.Chem.Soc.108. (1986)

J.Am.Chem.Soc.108。

Inorg.Chem.25. (1986)

Inorg.Chem.25。

Inorg. Chem.25. (1986)

无机物。