1993 Fiscal Year Final Research Report Summary
The highly selective carbon-carbon bond formation by organoboron reagents
| 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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| Keywords | Cross-coupling / Haloboration / Allyboration / Benzylboronate / Allyboronate / o-Quinodimethane / Palladium-catalyst / Propargyl carbonate |
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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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