DEVELOPMENT OF NEW NMR TECHNIQUES AND THEIR APPLICATION TO STRUCTURAL ANALYSIS OF NATURAL PRODUCTS

新核磁共振技术的开发及其在天然产物结构分析中的应用

• 批准号: 06556019
• 负责人: SETO Haruo
• 金额: $ 9.22万
• 依托单位: INSTITUTE OF MOLECULAR AND CELLULAR BIOSCIENCES,UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06556019/
• 关键词: decoupled-HMBC; D-HMBC; MolSkop; TANGO-HMBC; analysis of stereo-structures by computer calculation; プロモインドシン; スタキボシン; プロモチオシン; ゲニンチオシン; セコスリキサイド; コンピュータによる立体構造解析

In this project, we have investigated the applications of a new NMR technique called decoupled-HMBC (D-HMBC) developed by our group to structural analysis of complicated natural products. In addition, we have carried out analysis of stereo-structures by computer calculations using a newly developed software program (MolSkop) by the JEOL group.As a result, D-HMBC has turned out to be an excellent method to observe small long-range ^<13>C-^1H couplings, which can not be detected by hitherto available techniques. In addition, we have improved the data processing procedures ; ood NMR spectra with improved signal to noise ratio were obtained when data processing was made by the phase sensitive mode of the t2 axis data and by power mode of the t1 axis data.Comparison of this new technique (D-HMBC) with the pulse field gradiet (PGF) technique has revealed that PFG is superior to D-HMBC in most cases, but when the signal intensities were considerably affected by J-modulation caused by ^1H-^1H spin couplings, D-HMBC gave better results and so a method of choice in such situation. In this project, we have established experimental conditions for obtaining good D-HMBC spectra. This technique has been implemented to commercially available NMR instruments is now being used by some groups.We have improved the MolSkop software program and proved that it is a useful method to structural analysis of complicated polycyclic systems.In addition, we have recently developed a new technique called TANGO-D-HMBC,which is quite useful for detecting ^<13>C-^<13>C couplings separed by two bonds. Such kinds of long-range ^<13>C-^<13>C couplings were hardly observed by other methods. This pulse sequence is quite useful for datailed analysis of the ^<13>C- labeling pattern with microbial products formed by arrangement of the carbon skeleton.

本课题研究了本课题组开发的一种新的核磁共振技术--此外，我们还使用JEOL小组新开发的软件程序（MolSkop）通过计算机计算进行了立体结构分析，结果表明，D-HMBC是观察迄今为止无法检测到的小的长程^ C-^1H偶合的一种很好的方法<13>。此外，我们还改进了数据处理程序;采用t_2轴相敏模式和t_1轴功率模式进行数据处理，得到了信噪比较好的NMR谱，并与脉冲场梯度（PGF）技术进行了比较，结果表明，脉冲场梯度技术在大多数情况下上级D-HMBC，但当信号强度受到^1H-^1H自旋耦合引起的J调制的显著影响时，D-HMBC给出了更好的结果，因此是这种情况下的一种选择方法。在这个项目中，我们已经建立了获得良好的D-HMBC光谱的实验条件。我们改进了MolSkop软件程序，证明它是一种用于复杂多环体系结构分析的有效方法.此外，我们最近发展了一种新的技术TANGO-D-HMBC，它对检测由两个键组成的^<13>C-^<13>C偶合反应非常有用.用<13><13>其他方法很难观察到这种长程^ C-^ C偶合。该脉冲序列对于<13>通过碳骨架排列形成的微生物产物的13 C-标记模式的数据化分析非常有用。

项目成果

K. Ogawa, M. Nakamura, H. Seto et al.: "Stachybocins, novel endothelin receptor antagonists, produced by Stachybotrys sp. M6222. II. Structure determination of stachybocins A, B and C." J. Antibiotics. 48. 1396-1400 (1995)

K. Okawa、M. Nakamura、H. Seto 等人：“Stachybocins，新型内皮素受体拮抗剂，由 Stachybotrys sp. M6222 产生。II. Stachybocins A、B 和 C 的结构测定。”

B.-S.Yun and H.Seto: "Promoinducin, a novel thiopeptide produced by Streptomyces sp. SF2741." Biosci.Biotech.Biochem.59. 876-880 (1995)

B.-S.Yun 和 H.Seto：“Promoinducin，一种由链霉菌 SF2741 产生的新型硫肽。”

B.-S.Yun,H.Seto et al.: "Microbial metabolites with tipA promoter inducing activity.II.Geninthiocin,a novel thiopeptide produced by Streptomyces sp." J.Antibiotics. 47. 969-975 (1994)

B.-S.Yun、H.Seto 等人：“具有tipA启动子诱导活性的微生物代谢物。II.Geninthiocin，一种由链霉菌属产生的新型硫肽。”

B.-S.Yun, T.Hidaka, K.Furihata and H.Seto: "Promothiocins A and B,novel thiopeptides with a tipA promoter inducing activity produced by streptomyces sp. SF2741." J.Antibiot. 47. 510-514 (1994)

B.-S.Yun、T.Hidaka、K.Furihata 和 H.Seto：“Promothiocins A 和 B，新型硫肽，具有由链霉菌 SF2741 产生的tipA启动子诱导活性。”

K. Shin-ya, S. Shimizu, H. Seto et al.: "Novel neuronal cell protecting substances, aestivopho enins A and B, produced by Streptomyces purpeofuscus." J. Antibiotics. 48. 1378-1381 (1995)

K. Shin-ya、S. Shimizu、H. Seto 等人：“新型神经元细胞保护物质，aestivopho enins A 和 B，由 Streptomyces purpeofuscus 产生。”