| Project/Area Number |
14078216
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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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| Review Section |
Science and Engineering
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| Research Institution | Kyoto University |
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Principal Investigator |
HAYASHI Tamio Kyoto University, Graduate School of Science, Professor, 大学院理学研究科, 教授 (00093295)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥25,600,000 (Direct Cost: ¥25,600,000)
Fiscal Year 2005: ¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 2004: ¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 2003: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2002: ¥6,000,000 (Direct Cost: ¥6,000,000)
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| Keywords | asymmetric catalysis / conjugate addition / asymmetric arylation / rhodium catalyst / chiral diene ligand / organoboron reagent / oraanozinc reagent / 触媒納不斉合成 / 不斉炭素-炭素結合形成 / 生理活性化合物 / 有機チタン試薬 / キラルジエン / 有機ホウ素化合物 / 有機チタン化合物 |
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| Research Abstract |
One of the most significant subjects for developing catalytic asymmetric reactions is the design and preparation of a chiral ligand which will fit in with a given reaction efficiently in catalytic activity and enantioselectivity. A number of chiral molecules containing phosphorus and/or nitrogen atoms have been prepared and used for transition metal-catalyzed asymmetric reactions, but they are not always useful as chiral ligands because of their low catalytic activity or enantioselectivity. In this research project, as conceptually new chiral ligands, we have introduced a series of chiral dienes which opened up a new dimension in the field of asymmetric catalysis. The chiral dienes are based on bicyclo [2.2.1] heptadiene (nbd^*), bicyclo [2.2.2] octadiene (bod^*), or bicyclo [3.3.1] nonadiene (bnd^*) skeleton. The chiral diene ligands were found to be very effective for rhodium-catalyzed asymmetric 1,4-addition of arylboron reagents to electron deficient olefins, 1,2-addition to N-sulfonylimines, and so on. The enantioselectivities observed with the chiral diene ligands are very high compared with those observed with other types of chiral ligands such as chiral bisphosphines. It is remarkable that the catalytic activity of the rhodium catalysts coordinated with the diene ligands is much higher than with conventional phosphorus ligands, which made it possible to realize the catalytic asymmetric reactions with a very small amount (<0.005 mol %) of the catalyst.
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