1999 Fiscal Year Final Research Report Summary
New Radical Reactions by Means of Trialleylmanganate
| 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)
|
|---|
| Project Period (FY) |
1997 – 1999
|
| Keywords | manganese ate complex / Ringle electron transfer / radical cydigation / dibromo compound / α-iodo acetal / actioe manganese |
|---|
| 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.
|
