2003 Fiscal Year Final Research Report Summary
Synthetic application of carbon-carbon bond formations induced by group 9 metal catalyzed multi-component couplings
| Project/Area Number |
13450368
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | Nagoya University |
|---|
Principal Investigator |
MATSUDA Isamu Nagoya University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (80023266)
|
|---|
| Project Period (FY) |
2001 – 2003
|
| Keywords | rhodium complexes / CO incorporation / silylative cyclocarbonylation / lactone formation / lactam formation / allylic substitution / iridium complexes / propargylic substitution |
|---|
| Research Abstract |
This project focuses the development of carbon-carbon bond formation on the basis of multi-component coupling catalyzed by group 9 metal complex in one-pot procedure. Along the proposed strategy on rhodium-catalyzed reactions we successfully obtained the following results ; (1) the formation of bicyclo[3.3.0]octenone frameworks by the one-pot reactions among a hydrosilane, a 1,6-diyne, and CO and its application to the synthesis of hirsutene, (2) exploitation of a new method for the construction of 4,5, and 6-membered lactones by the incorporation of CO into alkynylalcohols and transformation of spiro-type γ-lactones to bicyclic ketones, (3) exploitation of a new method for the construction of 4,5,6, and 7-membered lactams by the incorporation of CO into alkynylamines, and (4) annulative long range silylformylation of hept-1-ene-6-ynes. We also realized a new three-component coupling under neutral conditions as follows ; formal hydrocarbamoylation and hydroallylation toward electron-deficient alkenes and a new Mannich type coupling triggered by the oxydative addition of a hydrosilane to low-valent rhodium metal. It was also revealed that an Ir-cationic complex shows strong Lewis acidity in CH_2Cl_2 and behaves as an efficient catalyst for aldol coupling, Michael type coupling, direct substitution of allylic alcohols and selective substitution of propargylic esters in reactions involving enoxy silane as a nucleophile.
|
