Unity between Inverse Phase Transfer Catalyst and Transition Metal Catalyst

用过渡金属膦配合物催化有机分子与疏脂试剂的反应，需要使用两亲性溶剂或加入相转移催化剂。然而，这些方法污染了水排水，并且对催化剂与产物的分离没有影响。在这个项目中，我们试图通过反相转移催化剂和过渡金属催化剂的统一来解决这些问题。在双相条件下，钯的水溶性膦配合物在羰基化合物与氯丙烯或烯丙醇与SnCl_2的烯丙化反应和芳基碘化物与NaCN的氰化反应中起反相转移催化剂的作用。PdCl_2L_2 （L=PPh_2 (m-C_6H_4SO_3Na)）在庚烷中的催化效率高于甲苯和苯甲醚。PdCl_2L_2在氰化反应中的催化活性依次升高；L = P(甲苯基)_2 (3-C_6H_3 (4-Me) SO_3Na] > PPh_2 [3-C_6H_3 (4-Me) SO_3Na] > PPh_2 (m-C_6H_4SO_3Na) > PPh (3-C_6H_3 (4-Me) SO_3Na] _2 > P [3-C_6H_3 (4-Me) SO_3Na] _3。这些双相反应使用水溶性催化剂，使我们很容易分离产物和催化剂，并从反应混合物中回收溶剂。

The catalytic reactions of organic molecules with lipophobic reagents using phosphine complexes of transition metals require using amphiphilic solvents or adding phase transfer catalysts. However these pollute the aqueous drainage, and these methods are no effect on the separation of the catalyst from the products. In this project, we tried to solve these problems by the unity between inverse phase transfer catalyst and transition metal catalyst. The water-soluble phosphine complexes of palladium acted as the counter phase tranfer catalysts in the allylation of carbonyl compounds with allyl chlorides or allyl alchols and SnCl_2 and in the cyanation of aryl iodides with NaCN under biphasic conditions. The catalytic efficiency of PdCl_2L_2 (L=PPh_2 (m-C_6H_4SO_3Na)) was higher in heptane than in toluene or anisole. The catalytic activity of PdCl_2L_2 in the cyanation increased in the following order ; L=P (tolyl) _2 [3-C_6H_3 (4-Me) SO_3Na] >PPh_2 [3-C_6H_3 (4-Me) SO_3Na] >PPh_2 (m-C_6H_4SO_3Na) >PPh [3-C_6H_3 (4-Me) SO_3Na] _2>P [3-C_6H_3 (4-Me) SO_3Na] _3. These biphasic reactions using the water-soluble catalysts allowed us easily to separate the product and the catalyst, and to recover the solvent from the reaction mixture.