| Project/Area Number |
04453091
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | (Faculty of Engineering) Hokkaido University |
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Principal Investigator |
SUZUKI Akira Hokkaido Univ., Fac. of Eng., Professor, 工学部, 教授 (40001185)
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| Co-Investigator(Kenkyū-buntansha) |
ISHIYAMA Tatsuo Hokkaido Univ., Fac. of Eng., Research Associate, 工学部, 助手 (00232348)
HAYA Shouji Hokkaido Univ., Fac. of Eng., Research Associate, 工学部, 助手 (20109490)
MIYAURA Norio Hokkaido Univ., Fac. of Eng., Associate Professor, 工学部, 助教授 (10002049)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1993: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1992: ¥3,500,000 (Direct Cost: ¥3,500,000)
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| Keywords | Cross-coupling / Haloboration / Allyboration / Benzylboronate / Allyboronate / o-Quinodimethane / Palladium-catalyst / Propargyl carbonate / 共役付加反応 / ビニル型ホウ素化合物 / ジエン合成 / ケトン合成 / 不斉合成 |
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| Research Abstract |
The cross-coupling reaction of organoboron compounds with organic halides, organic triflates, and propargyl carbonates are studied. The palladium-catalyzed cross-coupling reaction of organoboron compounds provides a general and convenient method for the synthesis of stereodefined alkenes, alkedienes or alkenynes, biaryls, and vinylic sulfides. The similar coupling reaction under carbon monoxide (1 atm) produces alkyl vinyl ketones, alkyl aryl ketones, alkyl alkyl ketones and biaryl ketons in excellent yields.
The palladium-catalyzed cross-coupling reaction of the Knochel's borylmethylzindc reagent with 1-alkenyl or aryl halides provided the corresponding allylic or benzylic boronates in excellent yields. The procedures were applied for the first intramolecular allylboration of aldehyds or ketones, and the generation of o-quinodimetane via the boron rearrangement.
Haloboration of terminal alkynes with boron tribromide followedby one carbon homologation provided a convenient and stereoselective method for synthesis of beta, beta-derivatives of these allylic boranates produced homoallylic alcohols having quanternary carbon with high enantioselectively over 94% ee.
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