Unity between Inverse Phase Transfer Catalyst and Transition Metal Catalyst

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添加相转移催化剂。然而，这些方法污染了水性排水，并且这些方法对催化剂与产物的分离没有影响。本课题试图通过反相转移催化剂与过渡金属催化剂的结合来解决这些问题。在两相条件下，水溶性钯膦配合物对羰基化合物与烯丙基氯或烯丙醇和SnCl_2的烯丙基化反应和芳基碘与NaCN的氰化反应具有反相转移催化作用。PdCl_2L_2（L=PPh_2（m-C_6 H_4SO_3 Na））在庚烷中的催化效率高于在甲苯和苯甲醚中的催化效率。PdCl_2L_2对氰化反应的催化活性依次为：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_6 H_4SO_3 Na）>PPh [3-C_6H_3（4-Me）SO_3Na] _2>P [3-C_6H_3（4-Me）SO_3Na] _3。这些使用水溶性催化剂的两相反应使我们能够容易地分离产物和催化剂，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.