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

光学活性的四齿18元冠硫醚Binaph_2Me_4 [18] S_4（含两个C_2轴不对称的1，1 '-联萘）和四齿17元BinaphMe_6 [17] S_4和三齿13元BinaphMe_4 [13] S_3（含一个1，1'-联萘），的对映选择性合成和它们的结构明确阐明了通过X-射线分析。合成了Rh（I，III），Ru（II），Pd（II），Pt（II）和Ni（II）与手性二萘甲基硫代苯（BinaphMe_6 [17] S_4）和二萘甲基硫代苯（BinaphMe_4 [13] S_3）的配合物。由于1，1 '-联萘部分的枢轴键的内在扭曲，联萘_2Me_4 [18] S_4与金属离子形成平面配位，形成D_2对称的双螺旋Sq平面和Oh配合物。BinaphMe_6 [17] S_4的单螺旋和双螺旋OH配合物具有up-up-up-down和up-down-up-down构象，其中up-down和up-down表示S原子上的孤对轨道相对于赤道4S平面的方向，它们的构象受中心金属和轴向配体的影响。研究了这些螺旋状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Grignard偶联反应，揭示了它们作为不对称催化剂的能力以及螺旋腔区分手性的能力，并考察了1，1 '-联萘基团和环成员数对螺旋腔区分手性的影响.

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.