摘要/Abstract

1,1'-螺二氢茚骨架是在21世纪初发展起来的一类新型手性配体或催化剂的骨架, 具有C₂对称性, 以及刚性强、稳定性高、易于修饰等特点. 周其林等将手性1,1'-螺二氢茚-7,7'-二酚(SPINOL)发展为一系列螺环配体及催化剂, 在催化不对称合成领域获得了巨大的成功. 1,1'-螺二氢茚骨架的配体及催化剂被认为是为数不多的“优势手性配体和催化剂”. 尽管催化的不对称合成已经出现, 目前方法得到的SPINOL及类似物多为外消旋体, 需要进行费力的手性拆分. 合成和拆分步骤繁琐的局限性对其大规模生产形成了阻碍. 因此, 如何从廉价易得的原料出发, 发展相应手性螺环骨架配体的高效、不对称催化合成新方法, 是非常迫切而且具有挑战性的课题. 总结了最近20年SPINOL及螺环骨架类似化合物的合成方法, 包括含杂原子的螺环骨架, 希望能对配体或催化剂用途的螺环骨架的构建有所启发.
关键词: 1,1'-螺二氢茚-7,7'-二酚(SPINOL), 螺环骨架构建, C₂对称性配体, 手性拆分
1,1'-Spirobiindane possesses a new type of skeleton for chiral ligands developed in the early 21st century, which has the characteristics of C₂-symmetry, strong rigidity, high stability, and ease of modification. Zhou et al. developed 2,2',3,3'-tetrahydro-1,1'-spirobi[1H-indene]-7,7'-diol (SPINOL) into series of chiral ligands and catalysts, and achieved great success in the field of catalytic asymmetric synthesis. These ligands and catalysts bearing 1,1'-spirobiindane skeleton are considered as few “privileged chiral ligands and catalysts”. Though catalytic asymmetric syntheses have appeared, in the present methods SPINOL and analogues are usually obtained in racemic forms, which require further chiral resolution. Laborious synthetic and resolution steps limit their productions in industrial scale. Therefore, it is urgent as well as challenging to develop efficient method of asymmetric catalytic synthesis of chiral spiro ligands from cheap and readily available raw materials. The synthetic methods of SPINOL and analgoues in the past 20 years are summarized, including those bearing heteroatoms in the spiro skeleton, in the hope of sparking new ideas for the construction of spiro skeletons in ligands or catalysts.
Key words: 2,2',3,3'-tetrahydro-1,1'-spirobi[1H-indene]-7,7'-diol (SPINOL), construction of spiro skeleton, C₂-symmetric ligand, chiral resolution


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