光学的な二重螺旋クラウンチオエーテル遷移金属錯体の合成と不斉識別

对映体选择性地合成了具有光学活性的18元冠醚四元联苯醚(Binaph_2Me_4[18]S_4)、17元联萘联Me_6[17]S_4和含酮1，1‘-联萘1基的三齿13元联萘Me_4[13]S_3，其结构经X-射线分析确证。合成了Rh(I，III)、Ru(II)、Pd(II)、Pt(II)和Ni(II)与手性联膦Me_2Me_4[18]S_4、联胺Me_6[17]S_4和联胺Me_4[13]S_3的配合物。由于1，1‘-联萘基团枢轴键的固有扭曲，完全预先构筑了与金属离子平面配位的联二磷酸盐[18]S_4，得到了具有D_2对称性的双螺旋平面型和羟基型配合物。双核Me_6[17]S_4得到了具有向上-向下和向上-向下-向上-向下构象的单螺旋和双螺旋羟基配合物，其中向上和向下表示S原子上孤对轨道相对于赤道4S平面的方向，它们的构象受到中心金属和轴向配体的影响。考察了这些螺旋Rh(I，III)和Ni(II)配合物催化的酮的不对称硅氢化反应和不对称格氏交叉偶联反应，揭示了这些螺旋硫化物作为不对称催化剂的能力和螺旋空腔识别手性的能力，这一能力受1，1‘-联萘基团和环元数目的影响。

Optically active quadridentate 18-membered crown thioether, Binaph_2Me_4 [18] S_4, incorporating two C_2-axially dissymmetric 1,1'-binaphthyl groups, and quadridentate 17-membered BinaphMe_6 [17] S_4 and tridentate 13-membered BinaphMe_4 [13] S_3, incorporating one 1,1'-binaphthy1 group, were enantioselectively synthesized and their structures were elucidated unequivocally by an X-ray analysis. The Rh (I,III), Ru (II), Pd (II), Pt (II), and Ni (II) complexes with these chiral Binaph_2Me_4 [18] S_4, BinaphMe_6 [17] S_4 and BinaphMe_4 [13] S_3 ligands were prepared. Binaph_2Me_4 [18] S_4 was fully preorganized for a planar coordination to metal ions due to the inherent twist about pivotal bonds of 1,1'-binaphthyl moieties to afford doubly helical Sq.planar and Oh complexes of D_2 symmetry. BinaphMe_6 [17] S_4 gave singly and doubly helical Oh complexes with up-up-up-down and up-down-up-down conformations where up and down indicate the direction of lone pair orbitals on the S atom with respect to the equatorial 4S plane, and their conformations were influenced by central metals and axial ligands. Asymmetric hydrosilylation reaction of ketones and asymmetric Grignard cross-coupling reaction catalyzed by these helical Rh (I,III) and Ni (II) complexes were examined to reveal the ability of these sulfur helicates as asymmetric catalysts and the capability of the helical cavity discriminating te chirality, which was affected by the number of 1,1'-binaphthyl moieties and ring members.