| Project/Area Number |
05236101
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Research Institution | Tohoku University |
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Principal Investigator |
YAMAMOTO Yoshinori Tohoku University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (60029519)
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| Co-Investigator(Kenkyū-buntansha) |
NARASAKA Koichi The University of Tokyo, School of Science, Professor, 大学院・理学系研究科, 教授 (50016151)
SONODA Noboru Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (20083983)
SUZUKI Hitomi Kyoto University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (50025342)
KOSUGI Masanori Gunma University, Faculty of Engineering, Professor, 工学部, 教授 (60008464)
ANDO Wataru University of Tsukuba, Department of Chemistry, Professor, 化学系, 教授 (30008429)
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| Project Period (FY) |
1993 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥68,800,000 (Direct Cost: ¥68,800,000)
Fiscal Year 1995: ¥23,400,000 (Direct Cost: ¥23,400,000)
Fiscal Year 1994: ¥23,400,000 (Direct Cost: ¥23,400,000)
Fiscal Year 1993: ¥22,000,000 (Direct Cost: ¥22,000,000)
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| Keywords | Hydrocarbonation reaction / Carbanion / Allene / Palladium catalyst / Silyl anion / omicron-Quinodimethane / Bismuthonium salts / Telluru-lithium exchange reaction / 遷移金属触媒 / 有機金属化合物 / 付加反応 / 立体選択的反応 / 位置選択的反応 / 有機ケイ素化合物 / キラルアンモニア / β-ラクタム / スズ化合物 / 有機リチウム試薬 / 金属酸化剤 / 有機ビスマス化合物 / 金属アミド / アミドクプラート / 有機スズ化合物 / 有機テルル化合物 / ラジカル |
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| Research Abstract |
Pronucleophiles (H-Nu) add to the carbon-carbon double bond of allenes in the presence of a palladium catalyst to give the corresponding olefins in good to high yields (hydrocarbonation reaction). The regiochemistry of the addition depends upon the substituent of allenes ; dialkyl, aryl, and monoalkylallenes give the terminal (g) adducts, arylallenes bearing an electron withdrawing group at the para-position of aromatic group produce the internal (beta) adducts, and alkoxy (or phenoxy) allenes afford the a-adducts. The palladium catalyzed addition of H-Nu to sulfur substituted allenes, allenylsulphides, gives the g-addition products in good to high yields. This regioselectivity is in marked contrast with that of the oxygen substituted allenes.
Although Wurtz coupling reaction of 9,10-dichloro-9,10-dimethyl-9,10-disilaanthracene with sodium in toluene at 110 ﾟC formed bridged dimer in only 7 % yield, the increased yields of the dimer have been achieved by direct reaction of 9,10-dihydro-9,10-dimethyl-9,10-disilaanthracene with lithium.
Thermolysis of o- (3-trifuluoroacetyloxy-1-propenyl) benzyltributylstannane at 80 ﾟC gave a-vinyl-o-quinodimethane, which reacted with dienophiles to afford Diels-Alder adducts with two stereoisomers in good yield.
First synthesis, X-ray structure analysis and reaction of alkenyltriphenylbismuthonium salts were studied.
Organotellurium compounds readily undergo Te-Li exchange to give a variety of organolithium compounds which include highly reactive and unstable reagents such as acyl-, aroyl-, and carbamoyl-lithiums.
The selective preparation of unsymmetrical ketones and a-diketones was accomplished by the reaction of decacarbonyldimanganese (Mn2 (CO) 10) with two kinds of alkyllithiums.
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