Mandai Hiroki, Fujii Kazuki, Yasuhara Hiroshi, Abe Kenko, Mitsudo Koichi, Korenaga Toshinobu, Suga Seiji
Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan.
Faculty of Engineering, Department of Chemistry and Bioengineering, Iwate University, Morioka, Iwate 020-8551, Japan.
Nat Commun. 2016 Apr 15;7:11297. doi: 10.1038/ncomms11297.
Catalysts that can promote acyl transfer processes are important to enantioselective synthesis and their development has received significant attention in recent years. Despite noteworthy advances, discovery of small-molecule catalysts that are robust, efficient, recyclable and promote reactions with high enantioselectivity can be easily and cost-effectively prepared in significant quantities (that is, >10 g) has remained elusive. Here, we demonstrate that by attaching a binaphthyl moiety, appropriately modified to establish H-bonding interactions within the key intermediates in the catalytic cycle, and a 4-aminopyridyl unit, exceptionally efficient organic molecules can be prepared that facilitate enantioselective acyl transfer reactions. As little as 0.5 mol% of a member of the new catalyst class is sufficient to generate acyl-substituted all-carbon quaternary stereogenic centres in quantitative yield and in up to 98:2 enantiomeric ratio (er) in 5 h. Kinetic resolution or desymmetrization of 1,2-diol can be performed with high efficiency and enantioselectivity as well.
能够促进酰基转移过程的催化剂对于对映选择性合成非常重要，近年来其发展受到了广泛关注。尽管取得了显著进展，但发现兼具稳定性、高效性、可回收性且能促进反应并具有高对映选择性，同时能够简便且经济高效地大量制备（即>10 g）的小分子催化剂仍然难以实现。在此，我们证明，通过连接一个经适当修饰以在催化循环的关键中间体中建立氢键相互作用的联萘基部分和一个4-氨基吡啶基单元，可以制备出异常高效的有机分子，这些分子能够促进对映选择性酰基转移反应。新催化剂类别的成员低至0.5 mol%就足以在5小时内以定量产率和高达98:2的对映体比例（er）生成酰基取代的全碳季碳立体中心。1,2-二醇的动力学拆分或去对称化也能够高效且具有对映选择性地进行。
