Practical Configuration Analysis for Natural Products.

天然产物的实用构型分析。

• 批准号: 10554043
• 负责人: MURATA Michio
• 金额: $ 8.26万
• 依托单位: Osaka University (1999-2000)The University of Tokyo (1998)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 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/en/grant/KAKENHI-PROJECT-10554043/
• 关键词: NMR; spin coupling constants; J values; configuration; conformation; natural products; maitotoxin; amphidinol; 鎖状構造

A method for elucidating the relative configuration of acyclic organic compounds was developed on the basis of carbon-proton spin-coupling constants and interproton spin-coupling constants. This method was developed for structural units represented by 2,3-or 2,4-disubstituted alkanes, where substituents were either dihydroxyl or methyl/hydroxyl groups. The basic theory of the methods is that, in acyclic systems, the conformation of adjacent asymmetric centers is represented by staggered rotamers, and their relative stereochemistry can be determined using these coupling constants because the combined use of the values enables the identification of the predominant staggered rotamer (s) out of the six possible ones derived from threo-and erythro-configuration. Detail conformational analysis for model and natural compounds, including maitotoxin, amphidinols and aflastatins, revealed that the method is practical for assignment of acyclic stereochemical centers.

发展了一种基于碳-质子自旋耦合常数和质子间自旋耦合常数的非环有机化合物相对构型的解析方法。该方法适用于以2，3-或2，4-二取代烷烃为代表的结构单元，其中取代基为二羟基或甲基/羟基。这些方法的基本理论是，在非环系统中，相邻不对称中心的构象由交错的旋转体表示，并且它们的相对立体化学可以用这些耦合常数来确定，因为结合使用这些值可以从三和红三环构型的六种可能的旋转体中识别出主要的交错旋转体(S)。对模型化合物和天然化合物的详细构象分析表明，该方法对于非环立体化学中心的归属是可行的。

项目成果

Iijima, K. et al.: "Identification of N^ω-carboxymethylarginine as novel acid-labile advanced glycation and product in collagen"Biochemical. J.. (in press). (2000)

Iijima, K. 等人：“N^ω-羧甲基精氨酸作为胶原蛋白中新型酸不稳定高级糖基化和产物的鉴定”，《Biochemical》（出版中）。

Ikeda,H.: "Absolute configuration of alfatoxin A, a specific inhibitor of aflatoxin production by Aspergillus parasiticus"J.Org.Chem.. 65. 438-444 (2000)

Ikeda,H.：“黄曲霉毒素 A 的绝对构型，一种寄生曲霉产生黄曲霉毒素的特异性抑制剂”J.Org.Chem.. 65. 438-444 (2000)

泉川美穂: "^<18>O-labelling Pattern of Okadaic Acid from H_2 ^<18>O in Dinoflagellate Prorocentrum lima Elucidated by Tandem Mass Spectrometry."Eur.J.Biochem.. 267. 5179-5182 (2000)

Miho Izumikawa：“通过串联质谱法阐明了甲​​藻原甲藻中 H_2 ^<18>O 的冈田酸的^<18>O-标记模式。”Eur.J.Biochem.. 267. 5179-5182 (2000)

Matsumori,N.: "Stereochemical determination of acyclic structures based on carbon-proton spin-coupling constants"J.Org.Chem.. 64. 866-876 (1999)

Matsumori,N.：“基于碳-质子自旋偶联常数的无环结构的立体化学测定”J.Org.Chem.. 64. 866-876 (1999)

赤坂和昭: "Absolute Configuration of a ceramide with a Novel Branched-chain Fatty Acid Isolated from the Epiphytic Dinoflagellate, Coolia monotis"Biosci. Biorech Biochem. 64. 1842 (2000)

Kazuaki Akasaka：“从附生甲藻中分离出的新型支链脂肪酸的神经酰胺的绝对构型”Biosci. 64. 1842 (2000)