1990 Fiscal Year Final Research Report Summary
Regioselective Oxygenation of Terminal Olefinic Carbon of 1-Alkenes
| Project/Area Number |
01550652
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
有機工業化学
|
|---|
| Research Institution | Osaka University |
|---|
Principal Investigator |
HOSOKAWA Takahiro Faculty of Engineering Science, Osaka Univ. Associate Professor, 基礎工学部, 助教授 (90029520)
|
|---|
| Project Period (FY) |
1989 – 1990
|
| Keywords | Terminal Olefin / Palladium Complexes / Molecular Oxygen / Allylamides / N-Allyllactams / Chelation |
|---|
| Research Abstract |
In this project, we have aimed to develop metal-catalyzed, regioselective oxygenation at terminal olefinic carbon of 1-alkenes with molecular oxygen For this purpose, we have chosen a concept that the regioselectivity will be controlled by introduction of substituents bearing an ability chelating metals into the allylic carbon. As expected, the regioselective oxygenation of the C-1 carbon of allylamides with O_2 to give the corresponding aldehydes (eq 1) was realized, when a catalyst system of PdCl_2(MeCN)_2 and CuCl was used in anhydrous aprotic solvents such as ClCH<_2CH_2Cl containing Hexa-Methyl-Pphosphor-Amide (HMPA). This makes a sharp contrast with the usual Wacker oxidation. Thus, addition of water to the aforementioned system gave methyl ketones exclusively which arises from nucleophilic attack of H_2O onto the C-2 carbon of allylamides. Similar observations were resulted with N-allyllactams and its analogues. The oxygenation of N-allylamides at the C-1 carbon with O_2 to give aldehydes which was developed in this project provides the first example in the field of metalcatalyzed oxidation of alkenes.
|
