| Project/Area Number |
20580108
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Bioproduction chemistry/Bioorganic chemistry
|
|---|
| Research Institution | The University of Tokyo |
|---|
Principal Investigator |
FURIHATA Kazuo The University of Tokyo, 大学院・農学生命科学研究科, 助教 (20219091)
|
|---|
| Project Period (FY) |
2009 – 2011
|
| Project Status |
Completed (Fiscal Year 2010)
|
| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2010: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2009: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2008: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
|
|---|
| Keywords | long range JCH / Selective J-resolved HMBC / Selective J-resolved HMQC / Selective COSY-J-resolved HMBC / 遠隔スピン結合 / J-resolved HMBC / Bird-J-resolved HMBC / J-resolved HMQC / selective J-resolved HMQC / High orderスピン系 / HETLOC / selective excitation |
|---|
| Research Abstract |
In order to observe long range JCH couplings and JHH couplings, we have developed Selective J-resolved HMBC, Selective COSY-J-resolved HMBC and Selective J-resolved-HMQC.
Selective J-resolved HMBC
Determination of long-range C-H couplings (JC-H) is getting important for stereochemical studies of natural products. The J-resolved HMBC-1 method is a method of choice for this purpose with high sensitivity. The shapes of cross peaks, however, become complex by H-H couplings and long-range JC-H resulting in difficult analysis of complicated spin systems. In order to overcome these problems associated with J-resolved HMBC-1, we have developed a new technique, Selective J-resolved HMBC. The new method incorporating proton-proton decoupling into J-resolved HMBC-1 enables to suppress JH-H and to observe only long-range C-H couplings with complicated molecules having short T2.
Selective COSY-J-resolved HMBC
We present an improved version named Selective COSY-J resolved HMBC. This method enhances the
… More
sensitivity of cross peaks of methine proton signals attached to a methyl group in J-resolved HMBC or Selective J-resolved HMBC, and enables to determine its long range JCH couplings. J-resolved HMBC or Selective J-resolved HMBC were developed for observation of long range JCH couplings by the J-scaling pulse sequence into HMBC. Application of this new technique to model compounds, portmicin and monazomycin, proved that this method is useful for determination of JC H of complicated molecules.
Selective J-resolved HMQC
Analysis of H-H J coupling constants is important for relative stereochemical studies of natural organic compounds. Overlapping protons or strongly coupled protons make analysis of H-H J coupling constant difficult. This problem can be solved by utilizing a proton attached to 13C. In a strongly coupled HA and HB spin system, HA attached to 13C and HB connected to 12C constitute a week coupled proton system resulting in a large chemical shift difference between HA and HB spread by CA-HA J-coupling. Thus the HA-HB J constant can be clearly determined by analyzing HA. In order to overcome this problem, we developed a new method, selective J-resolved HMQC by decoupling two adjacent protons. Application of this method to a model compound, monazomycin with a complicated structure proved its effectiveness for stereochemical studies. Less
|
