| Budget Amount *help |
¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 2003: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2002: ¥2,800,000 (Direct Cost: ¥2,800,000)
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| Research Abstract |
With growing awareness in industry for sustainable development, it is obviously required to find environmentally friendly synthetic process. In the present study, focus was place on the use of molecular oxygen in air as the oxydizing agent in order to develop environmentally benign synthetic organic reactions by using organometallic as the catalyst under mild conditions, and the combination of Pd^<+2> Cu^<+2> was chosen as the catalyst from the following viewpoint. The activation of molecular oxygen is enforced on the Cu atom of Pd-Cu bimetallic catalyst, and the 0 atom of 0_2 is allowed to transfer onto the alkene coordinated to Pd. Our preliminary study led us to find that this process was realized by using a Pd-Cu-hexamethylphosphoramide (HMPA) catalyst, which was produced via self-organization of Pd^<+2> and Cu salts with HMPA. In order to expand the scope and limitation of this result, we have firstly prepared, in the present study, various Pd-Cu bimetallic complexes bearing amide
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s and ureas. Secondary, we have studied the regioselectiye oxidation of terminal alkenes at C_1 carbon with 0_2, which is catalyzed by Pd-Cu bimetallic complexes. As the result, we have found that the regioselective oxidation of this type is attained with allylic compounds bearing cyclic amides, and the selectivity decreases with decreasing the ring size of 6>5>4. Furthermore, we have systematically studied the aldehyde formation from simple terminal alkenes, such as 1-decene, by the use of alcohols as uncleophile under the conditions using a combination of PdCl_2(CH_3CN)_2 and CuCl_2 as a catalyst in l,2-dimethoxyethane (DME) under an atmosphere of 0_2. As the result, we have found that the selectivity of aldehyde formation increases with increasing the steric bulkiness of MeOH > EtOH > i-PrOH> t-BuOH, but that the yield of aldehyde concurrently decreases in this order. Accordingly, if t-BuOH is utilized as the nucleophile, the reactivity of Pd catalyst must be improved in further study. Less
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