| Project/Area Number |
06453140
|
|---|
| 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 |
TANAKA Hideo Okayama Univ., Dept.of Applied Chemistry, Associate Professor, 工学部, 助教授 (60032950)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
GENBA Akiko Okayama Univ., Dept.of Applied Chemistry, Research Associate, 工学部, 教務員 (80274009)
OKUMOTO Hiroshi Kurashiki Univ.of Science and Arts Dept.of chemical Technology, Associate Profes, 産業科学技術学部, 助教授 (90183251)
KUROBOSHI Manabu Okayama Univ., Dept.of Applied Chemistry, Lecturer, 工学部, 講師 (30242316)
|
|---|
| Project Period (FY) |
1994 – 1996
|
| Project Status |
Completed (Fiscal Year 1996)
|
| Budget Amount *help |
¥7,400,000 (Direct Cost: ¥7,400,000)
Fiscal Year 1996: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1995: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1994: ¥4,600,000 (Direct Cost: ¥4,600,000)
|
|---|
| Keywords | Organotin / Copper (I) Salt / Alkenyl Copper / Bimetal Reagnet / Copper (0) / 3-Alkenylcephem / C-C Bond Formation / Copper System / 銅(O) / アルケニ銅 / 3-アルケルセフェム / 炭素-炭素結合形式 |
|---|
| Research Abstract |
Generation of organocopper species in organotin/copper (I) chloride systems and applicatoins t to new carbon-carbon bond formaiton have been investigated. The generation and reaction of alkenylcopper (I) species in alkenyltins/copper (I) chloride/NMP systems could open new synthetic routes to 3-alkenyl-DELTA^3-cephems and 3-alkenyl-DELTA^2-cephems, respectively. The presence of bipyridine or terpyridine in the reaction media stabilized the copper species effectively to promote alkenylation of 3-chloromethylcephem. Similar copper (I) species could be generated by direct reaction of allylic or benzylic halides with copper powder in NMP in the presence of bipyridine or terpyridine. Homocoupling and heterocoupling of 3-chloromethyl-cephem were successfully achieved by use of the in situ generated copper species.
A combination of tin hydride and copper (I) chloride in NMP was also investigated, in which, coordinatively unsaturated copper (I) hydride species were formed. Reaction of the in situ generated copper (I) hydride with allenecarboxylate, alkenyl triflate, and allylic halides proceeded smoothly to offer new synthetic schemes of 3-norcephem, its DELTA^2-isomer, and 3-exo-methylenecepham. The organocopper species innovated in this research project are far different from those preapred by the conventional methods. Further applications of the organocopper species are now in progress.
|
