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
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nagoya University |
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Principal Investigator |
MATSUDA Isamu Nagoya University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (80023266)
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| Project Period (FY) |
2001 – 2003
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| Keywords | rhodium complexes / CO incorporation / silylative cyclocarbonylation / lactone formation / lactam formation / allylic substitution / iridium complexes / propargylic substitution |
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| 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.
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Research Products
(14 results)
