| Project/Area Number |
13650925
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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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 | Kochi University of Technology |
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Principal Investigator |
HOSOKAWA Takahiro Kochi Univ. of Tech. Fac. Eng. Professor, 工学部, 教授 (90029520)
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| Co-Investigator(Kenkyū-buntansha) |
SHIGA Akinobu Sumitomo Chemical Co. Ltd Head Researcher, 室長研究員
KOBIRO Kazuya Kochi Univ. of Tech. Fac. Eng. Associate Professor, 工学部, 助教授 (60170370)
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| Project Period (FY) |
2001 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2002: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2001: ¥2,600,000 (Direct Cost: ¥2,600,000)
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| Keywords | allyl alcohol / cinnamyl alcohol / palladium(II) acetate / copper(II) acetate / catechol / molecular oxygen / tetrahydrofuran / ビニルエーテル / オキシパラジウム化 / ジヒドロフラン体 |
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| Research Abstract |
We have aimed to develop Pd^<2+>/Cu^<n+> catalysts of high performance in terms of reactivity and selectivity for the synthesis of fine chemicals. For this purpose, we have chosen Pd(II)- catalyzed coupling reaction of allylic alcohols and vinyl ethers in the presence of O2, which produces oxygen-containing heterocycles. Firstly, X-ray analysis of the product derived from cinnamyl alcohol and ethyl vinyl ether allowed us to determine it as the five-membered dihydrofuran. Secondary, incorporation of catechol into Pd(OAc)_2-Cu(OAc)_2 catalyst has been foun to give rise to a high catalytic activity in reactions involving a process of oxypalladation toward alkenes. With software called "LUMMOX" (Sumitomo Chemical Co. Ltd.) in computational chemistry, we have revealed that the high reactivity observed is due to the activation O_2 through catechol-copper complex. When the catalyst system developed here iwas used, ally alcohol itself reacts with vinyl ethers togive exomethylene tetrahydrofuran in more than 80% yield. Thirdly, we have found that the use of optically active 2, 2-bis[(4S)-4-benzyl-2-oxazoline] as the chiral source in the reaction of cinnamyl alcohol and ethyl vinyl ether
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