Catalyst Design Based on Functionalized Phosphines with a Compact Coordination Center
| Project/Area Number |
18350047
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | Hokkaido Univesity |
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Principal Investigator |
SAWAMURA Masaya Hokkaido Univesity, Faculty of Science, Professor (40202105)
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| Project Period (FY) |
2006 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥17,640,000 (Direct Cost: ¥15,600,000、Indirect Cost: ¥2,040,000)
Fiscal Year 2007: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000)
Fiscal Year 2006: ¥8,800,000 (Direct Cost: ¥8,800,000)
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| Keywords | homogeneous catalysts / heterogeneous catalysts / phosphines / hydrosilylation / hydrogenation / C-H activation / gold catalysts / alkynes / 高活性触媒 / 複素環式化合物 / アルキニルホスフィン / 固相担持ホスフィン / シリカ / 環化異性化 |
|---|
| Research Abstract |
1. Research with Caged Phosphine SMAP
The procedure for the synthesis of Ph-SMAP, the parent compound for various SMAP derivatives, was improved. It was confirmed that Ph-SMAP is an excellent ligand for hydrosilylation and hydrgenation of ketones.
SMAP was immobilized on silica gel surface. Silica-SMAP thus obtained showed very high ligand performance for the Rh-catalyzed hydrosilylation and hydrogenation of sterically demanding ketones.Furthermore, Silica-SMAP was successfully used for the development of Ir-catalyzed directed ortho borylation of functionalized arenes.
SMAP derivatives bearing an alkanethiol pendant at the bridgehead silicon atom was prepared and used for the preparation of self-assembled monolayer on gold surface. Au-SMAP thus prepared showed remarkably high activity and turnover efficiency in the Rh-catalyzed dehydrogenative alcohol silylation.
2. Research with Semihollow Trialkynylphosphines
Triethynylphosphine ligands with different end-cap groups were synthesized. Those with bulky end-caps showed unique coordination properties to form 1:1 metal-phosphine complexes selectively with various transition metal species. The semihollow-shaped triethynylphosphines showed extraordinally high accelerating effect in the Rh-catalyzed hydrosilylation of ketones. Furthermore, the semihollow triethynylphosphines were successfully used as ligands for gold-catalyzed alkyne cyclizations. In particular, the accelerating effect in the 6-exo-dig and 7-exo-dig cyclization was remarkable. In addition, this catalyst system enabled unprecedented cyclizations of internal alkyne derivatives.
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Report
(3 results)
Research Products
(99 results)
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[Journal Article] Cyclic Diaminocarbene-Rhodium(I) Complex Tethered to Disulfide : Synthesis and Application to Gold Surface Modification2006
Author(s)
Hara, K., Iwahashi, K., Kanamori, Y., Naito, S., Takakusagi, S., Uosaki, K., Sawamura, M.
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Journal Title
Chemistry Letters 35(8)
Pages: 870-871
NAID
Related Report
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