2005 Fiscal Year Final Research Report Summary
Organic Synthesis in Water Utilizing Inorganic Porous Materials
| Project/Area Number |
15350057
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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 | Osaka University |
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Principal Investigator |
MINAKATA Satoshi Osaka University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (90273599)
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| Co-Investigator(Kenkyū-buntansha) |
KOMATSU Mitsuo Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (60029197)
ODERAOTOSHI Yoji Osaka University, Graduate School of Engineering, Assistant Professor, 大学院・工学研究科, 助手 (60324810)
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| Project Period (FY) |
2003 – 2005
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| Keywords | Green Chemistry / Environmentally Organic Synthesis / Organic Synthesis in Water / Inorganic Porous Materials / Silica Gel / Aziridines / Water Soluble Nucleophiles / Ring Opening Reaction |
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| Research Abstract |
Although the use of PTC to permit the reaction in aqueous media is a general method, an alternative potential process in water was devised, based on the adsorptive nature of silica gel. While the application of silica gel to organic synthesis has been widely investigated, its use in organic reactions in aqueous media has not been exploited, to the best of our knowledge. Silica would be effective as organic reaction media in water because the organic molecule as a substrate would be adsorbed to the silica by hydrophobic interactions between the surface of the silica and the organic molecule. We investigated here on the iodine-catalyzed aziridination of olefins using Chloramine-T (CT) and the ring opening of the resulting aziridine in a silica-water system, in which the use of silica (silica gel vs. MCM-41) showed unique results. For example, when styrene was treated with CT, K_2CO_3, and a catalytic amount of I_2 in the presence of Silica Gel 60 in water, N-(p-toluenesulfonyl)-2-phenylaziridine was obtained in good yield. A variety of olefins were successfully employed in this silica-mediated olefin aziridination in water using the iodine catalyst-CT system. To show the generality of the present media in organic synthesis, the ring opening of N-(p-toluenesulfonyl)-2-n-hexylaziridine with NaN_3 or KCN was examined. The reaction of aziridines with NaN_3 or KCN in water in the absence of silica did not proceed similarly to the case of the aziridination described above. When Silica Gel 60 was added, however, the desired reaction proceeded to afford the regioselective ring-opening products, respectively. To obtain a ring expansion product by the system, potassium thiocyanate was employed in the reaction. As was expected, a ring expansion product, thiazolidine derivative consisting of one thiocyanate and two aziridines moieties was produced in good yield as a mixture of two diastereomers.
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