| Project/Area Number |
09450341
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | KYOTO UNIVERSITY |
|---|
Principal Investigator |
OSHIMA Koichiro Kyoto University, Department of Matial Chemistry, Professor, 工学研究科, 教授 (00111922)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
大嶌 幸一郎 京都大学, 工学研究科, 教授 (00111922)
忍久保 洋 京都大学, 大学院・工学研究科, 助手 (50281100)
|
|---|
| Project Period (FY) |
1997 – 1999
|
| Project Status |
Completed (Fiscal Year 1999)
|
| Budget Amount *help |
¥14,100,000 (Direct Cost: ¥14,100,000)
Fiscal Year 1999: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1998: ¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 1997: ¥7,100,000 (Direct Cost: ¥7,100,000)
|
|---|
| Keywords | manganese ate complex / Ringle electron transfer / radical cydigation / dibromo compound / α-iodo acetal / actioe manganese / gem-ジブロモアルカン / アリル化 / 低原子価金属 / グリニャ-ル反応剤 / 1,3-ジハロプロペン |
|---|
| Research Abstract |
1. Radical cyclization of ally1 2-iodopheny1 ether, N, N-dially1-2-iodoaniline by means of trialkylmanganate (II)
Treatment of 2-iodophenyl prenyl ether with tributylmanganate, generated from MnClィイD22ィエD2 and three molar amounts of butylithium, in THF afforded 3-isopropenyl-2, 3-dihydrobenzofuran in 88% yield. The reaction proceeds as follows. Single electron transfer from tributylmanganate to 2-iodophenol derivative would give an anion radical which generate phenyl radical under departure of the iodide anion. Exo-mode radical cyclization should afford tertiary carbon radical which recombines with n-BuMn to give the dialkylmanganese compound. Dehydromanganation would provide the final product.
2. Reaction of gem-dibromo compounds with trialkylmanganate
Dialkylation of gem-dibromocyclopropanes with trialkylmanganate was achieved. The reaction was initiated by bromine-manganese exchange. Then alkyl group would migrate from manganese to adjacent carbon under bromide elimination. The second alkylation by RX could provide the dialkylation products. The reaction was successfully applied to the preparation of alkenylsilanes starting from dibromomethyltrialkylsilanes.
3. Triallylmanganate-mediated cyclization of diyne, enyne, and diene.
Treatment of diyne with triallylmanganate provided bicyclized products containing a seven-membered ring. N,N-Bis (2-nonynyl) benzylamine gave a mixture of 9-benzyl-2, 6-dihexyl-9-azabicyclo [5. 3. 0] deca-1 (7), 2-diene, and 9-benzyl-2, 6-dihexyl-9-azabicyclo [5. 3. 0]-deca-1 (7), 3-diene, upon treatment with triallylmanganate.
|
