2000 Fiscal Year Final Research Report Summary
Development of novel carbon-carbon bond-forming reactions using α-phospnonovinyl carbanions
| Project/Area Number |
10450344
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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 | Kyushu Institute of Technology |
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Principal Investigator |
MINAMI Toru Kyushu Institute of Technology, Faculty of Engineering, Professor, 工学部, 教授 (10029134)
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| Co-Investigator(Kenkyū-buntansha) |
岡内 辰夫 九州工業大学, 工学部, 講師 (60274552)
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| Project Period (FY) |
1998 – 2000
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| Keywords | Vinyl anion / Vinylphosphonate / Vinylsilane / Vinylastannane / Vinyliodide / 炭素-炭素結合生成 |
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| Research Abstract |
We note the following results from this research :
(1) By using the β-heteroatom substituted vinylphosphonates, we succeeded in preparation of the novel α-phosphonovinyl carbanions, which were stabilized with steric hindrance and electron donating ability of β-heteroatom-substituents. Only a limited number of methods have been reported for the preparation of α-phosphonovinyl carbanions due to their lability. These results would be an approach to solve this problem.
(2) α-Lithiated vinylphosphonates were easily reacted with various electrophiles to give corresponding α-functionalized(R_3Sn, R_3Si, I) vinylphosphonates. Furthermore, we showed that the effect of additive such as Lewis acid and metal salt in this reaction. These results have indicated that these α-phosphonovinyl carbanions can serve a effective method for synthesis of multi-functionalized phosphorus compounds.
(3) It was found that α-silylated phosphonoketene dithioacetals were applied to Friedel-Crafts acylation due to catio
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n stabilizing effect of silyl and thio groups in the molecule. Moreover, α-silyl-β-(ethoxy)vinylphosphonate successfully underwent nuvleophilic substitution to afford β-substituted vinylphosphonate. These results demonstrates that nublephilic additon-elimination reaction could be applicable to functionalization at β-position of vinylphosphonates.
(4) Synthetic utilization of α-(triorganometal)- or iodo-substituted vinylphosphonates as heteroatom-substituted olefins was performed. It was found that α-silylated phosphonoketene dithioacetals were applied to Friedel-Crafts acylation due to cation stabilizing effect of silyl and thio groups in the molecule. Moreover, α-silyl-β-(ethoxy)vinylphosphonate sucessfully underwent nucleophilic substitution to afford β-substituted vinylphosphonate. These results demonstrates that nucleophilic addition-elimination reaction could be applicable to functionalization at β-position of vinylphosphonates. We achieved palladium-catalyzed cross-coupling reaction of α-stannyl and iodo-substituted vinylphosphonates and the successive C-C bond formation. These methods open a new way to synthesis of α-alkenyl and alkynylphosphonates. Less
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