2006 Fiscal Year Final Research Report Summary
Chiral Diene Ligands for Catalytic Asymmetric Reactions
| Project/Area Number |
16205013
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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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 | 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) |
2004 – 2006
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| Keywords | Chiral Diene Ligand / Catalytic Asymmetric Reactions / Conjugate Addition / Asymmetric Arylation / Rhodium Catalyst / Organoboron Reagent / Organozinc Reagent |
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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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[Journal Article] Rhodium-Catalyzed Asymmetric Synthesis of Indanones : Development of a New "Axially-Chiral" Bisphosphine Ligand2006
Author(s)
Shintani, R., Yashio, K., Nakamura, T.Okamoto, K., Shimada, T., Hayashi, T.
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Journal Title
J. Am. Chem. Soc. 128
Pages: 2772-2773
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Kinetic Studies Proving High Catalytic Activity of a Diene-Rhodium Complex in 1,4-Addition of Phenylboronic Acid to a,β-Unsaturated Ketones2006
Author(s)
Kina, A., Yasuhara, Y., Nishimura, T., Iwamura, H., Hayashi, T.
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Journal Title
Chem. Asian J. 1
Pages: 707-711
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] C2-Symmetric Bicyclo[3.3.1]nona-2,6-diene and Bicyclo[3.3.2]deca-2,6-diene. New Chiral Diene Ligands Based on 1,5-Cyclooctadiene Framework2005
Author(s)
Otomaru, Y., Kina, A., Shintani, R., Hayashi, T.
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Journal Title
Tetrahedron Asymmetry 16
Pages: 1673-1679
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Chira Phosphine-Olefin Bidentate Ligands in Asymmetric Catalysis : Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to Maleimides2005
Author(s)
Shintani, R., Duan, W.-L., Nagano, T., Okada, A., Hayashi, T.
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Journal Title
Angew. Chem. Int. Ed. 44
Pages: 4611-4614
Description
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[Journal Article] C2-Symmetric Bicyclo[2.2.2]octadienes as Chiral Ligands : Their High Performance in Rhodium-Catalyzed Asymmetric Arylation of N-Tosylarylimines2004
Author(s)
Tokunaga, N., Otomaru, Y., Okamoto, K., Ueyama, K., Shintani, R., Hayashi, T.
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Journal Title
J. Am. Chem. Soc. 126
Pages: 13584-13585
Description
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