| Project/Area Number |
12450365
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | OKAYAMA UNIVERSITY |
|---|
Principal Investigator |
TAKAI Kazuhiko Okayama University Department. Of Applied Chemistry, Faculty of Engineering Professor, 工学部, 教授 (00144329)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
OSHIKI Toshiyuki Okayama University Department of Applied Chemistry, Faculty of Engineering Lecturer, 工学部, 講師 (80311794)
|
|---|
| Project Period (FY) |
2000 – 2002
|
| Project Status |
Completed (Fiscal Year 2002)
|
| Budget Amount *help |
¥15,000,000 (Direct Cost: ¥15,000,000)
Fiscal Year 2002: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 2001: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2000: ¥9,700,000 (Direct Cost: ¥9,700,000)
|
|---|
| Keywords | Pinacol Coupling Reaction / Chromium(II) / One-Electro Reduction / α,β-Unsaturated Ketone / Allylic Chromium Reagent / Titanium(III) Complex / 1,2-Diol / Low-Valent Metal / ピナコール反応 / 交差カップリング反応 / マンガン / 立体化学制御 / 低原子価チタン / 3価チタン錯体 |
|---|
| Research Abstract |
The following stereoselective pinacol-type reactions are developed. (1) A cross-pinacol-type coupling reaction of α,β-unsaturated ketones and aldehydes is accomplished with CrCl_2 and Me_3SiCl in DMF. The diastereoselectivity of the reaction is proved to depend on the reaction temperature. (2) A cross-coupling reaction of oxygen-substituted dienes and aldehydes leading to 1,2-diol derivatives is performed with CrCl_2 in the presence of a catalytic amount of B_<12> and water. (3) A dl-selective pinacol-coupling reaction of aliphatic aldehydes is achieved with CrCl_2, manganese, and Me_3SiCl.
In addition, we collected information on the pinacol coupling reactions with low-valent metals. (1) A titanium(III) complex TiCl_3(tmeda)(thf) which is effective for a dl-selective pinacol-coupling of aromatic aldehydes, is isolated, and the molecular structure of the complex are examined by X-ray crystallographic analysis. (2) Titanium(III) and vanadium(III) complexes having a Tp ligand are isolated, and the structure of an aldehyde-coordinated vanadium(III) complex is determined by X-ray crystallographic analysis.
|
