Synthesis of Novel BINAP derivatives and their application
| Project/Area Number |
17550111
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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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 | Nara National College of Technology |
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Principal Investigator |
SHIMADA Toyoshi Nara National College of Technology, Department of Chemical Engineering, Professor, 物質化学工学科, 教授 (20303802)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2006: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2005: ¥2,100,000 (Direct Cost: ¥2,100,000)
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| Keywords | BINAP / Iodination / Axial Chirality / Cross-Coupling / Catalytic Asymmetric Synthesis / Fluorescence / Phenylene-ethynylene / ゾルゲル前駆体 / 量子収率 / 有機・無機ハイブリッド / 光学材料 / 不均一触媒 |
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| Research Abstract |
One of the most useful chiral phosphine ligands is 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), which exhibits high enantioselectivity in several types of asymmetric reactions including ruthenium-catalyzed hydrogenation and rhodium-catalyzed 1,4-addition and its related reactions. Over the last decade, there have been major efforts to prepare BINAP derivatives for recycling catalytic systems and achieving higher selectivity in asymmetric synthesis. Most of these BINAP derivatives have been prepared in several steps starting from 6-or 6,6'-substituted 1,1'-bi-2-naphthol. However, these derivatizations are inferior to direct functionalization of BINAP due to their low yields and associated handling losses. Here we report a new facile regioselective iodination at the 5,5'-position of BINAP and subsequent Sonogashira coupling reaction leading to the ethynyl-BINAP which is useful as a chiral ligand for a rhodium-catalyzed asymmetric 1,4-addition. Bis(pyridine)iodonium tetrafluoroborate was successfully used for regioselective iodination of BINAP dioxide to give 5,5'-diiodoBINAP dioxide in excellent yield of 92%, with no observed formation of 4,4'-diiodoBINAP dioxide. A Sonogashira cross-coupling reaction with 5,5'-diiodoBINAP dioxide gave the desired bis(phenylene-ethynylene) products in good yield. The resulting 5,5'-disubstituted BINAP dioxides have excellent fluorescent properties. Furthermore, we examined to transform 5,5'-disubstituted BINAP dioxides to sol-gel precursors with allylsilyl groups giving chirally photochemical materials. It is confidently expected that these chiral sol-gel precursors open the new field of material chemistry.
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Report
(3 results)
Research Products
(16 results)
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[Journal Article] Cubic phenylene bridged mesoporous hybrids from allylorganosilane precursors and their applications in Friedel-Crafts acylation reaction.2007
Author(s)
Kapoor, M.P., Kasama, Y., Yokoyama, T., Yanagi, M., Yokoyama, T., Inagaki, S., Shimada, T., Nanbu, H., Juneja, L.R.
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Journal Title
Microporous Mesoporous Mater. 101
Pages: 231-239
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Rhodium-Catalyzed Asymmetric Synthesis of Indanones : Development of a New "Axially Chiral" Bisphosphine Ligand.2006
Author(s)
Shintani, R., Yashio, K., Nakamura, T., Okamoto, K., Shimada, T., Hayash, 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] Self-assembly of cubic phenylene bridged mesoporous hybrids from allylorganosilane precursors.2006
Author(s)
Kapoor, M.P., Kasama, Y., Yokoyama, T., Yanagi, M., Inagaki, S., Shimada, T., Nanbu, H., Juneja, L.
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Journal Title
R.J.Mater.Chem. 48
Pages: 4714-4722
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Facile Preparation of a New BINAP-based Building Block, 5,5'-diiodoBINAP, and its Synthetic Application.2005
Author(s)
Shimada, T., Suda, M., Nagano, T., Kakiuchi, K.
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Journal Title
J.Org.Chem. 70
Pages: 10178-10181
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Facile Preparation of a New BINAP-based Building Block, 5,5'-diiodoBINAP, and its Synthetic Application2005
Author(s)
Shimada, T., Suda, M., Nagano, T., Kakiuchi, K.
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Journal Title
Journal of Organic Chemistry 70
Pages: 10178-10181
Related Report
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[Journal Article] An Alternate Route for the Synthesis of Hybrid Mesoporous Organosilica with Crystal-Like Pore Walls from Allylorganosilane Precursors.2005
Author(s)
Kapoor, M.P., Inagaki, S., Ikeda, S., Kakiuchi, K., Suda, M., Shimada, T.
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Journal Title
Journal of the American.Chemical Society 127
Pages: 8174-8178
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