1997 Fiscal Year Final Research Report Summary
Highly reactive and selective olefin carbometalation
| Project/Area Number |
08454196
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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 |
Organic chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
NAKAMURA Eiichi The University of Tokyo Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (00134809)
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| Project Period (FY) |
1996 – 1997
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| Keywords | allyl metal / hydrazone / carbometalation / organocuprate / computational study / asymmetric synthesis |
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| Research Abstract |
Addition of an organometallic reagent to an isolated olefin (olefin carbometalation reaction) is not only of synthetic interest but of mechanistic interest. Although the organometallic addition of carbonyl compounds has been a well-established chemistry, the olefin carbometalation reaction has been developed in rather limited araea owing to the lack of substantial p information on the reaction mechanism of the carbometalation reaction. In this reset, we developed new carbometalation reactions by using highly reactive and selective reagents. The experimental and theoretical results are listed below.
(1) Theoretical studies on the addition of polymetallic lithium organocuprate clusters to C-Cmultiple bonds was carried out with ab initio and density functional calculation. This study firstly provided detailed mechanisms of carfbocupration and 1,4-addition reaction, and revealed importance of cluster structure of the reagent.
(2) Highly enantioselective addition of organometallic reagent to C=N double bond was achieved by using optically active allylic zinc reagents which were developed during the study on enantioselective carbometalation reaction of an isolated olefin.
(3) Addition of metal enolate species to cyclopropenone acetal have been found in the course of the study on the olefin carbometalation reaction. The carbometalation product, cyclopropyl metal, was trapped by various electrophile. This is the first example of the addition of metal enolate to olefin and utilization of the intermediate organometallic species.
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