Creation of chiral interlayer catalytic system by use of straddled pillar complexes and inorganic layer crystal hosts

介绍了用我们新开发的“手性层间催化剂”进行的不对称加氢反应。一般来说，手性均相催化剂可以通过使用体积较大的配体固定手性构象来制备。由于均相催化体系的主要缺点是催化剂难以从产物中分离和回收，我们开发了一种新型催化剂，即将具有线性烷基链的手性Rh(I)柱配合物（跨界手性柱配合物）插入到锂带沸石（LiTN）中，合成了手性层间催化剂。我们发现柱状配合物中的长烷基链在层间呈线性链状，层间间距与链长成正比。用我们的新型手性层间催化剂，我们获得了超过相应的均相催化剂的不对称选择性和与均相催化剂相当的高活性。

The asymmetric hydrogenation using our newly developed "chiral interlayer catalysts" is described. Generally chiral homogeneous catalyst can be created by use of bulky ligands to fix the chiral conformation. Because the main drawback of the homogenous catalytic system is usually pointed out the difficulty in catalyst separation from the products and the recycling, we have developed a new type of catalysts, i.e., chiral interlayer catalysts have been synthesized by the intercalation of chiral Rh(I) pillar complexes (Straddled chiral pillar complexes) with linear alkyl chains into lithium taeniolite (LiTN). We found that the long alkyl chain groups in the pillar complexes were held between layers as a linear chain shape and the interlayer spacing was proportional to the chain length. By means of our novel chiral interlayer catalysts, we attained the asymmetry selectivity exceeding the corresponding homogeneous catalysts as well as the comparable high activity with the homogeneous ones.