School of Pharmaceutical Sciences , Sun Yat-sen University , Guangzhou 510006 , China.
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering , East China Normal University , Shanghai 200062 , China.
J Am Chem Soc. 2019 Jan 30;141(4):1473-1478. doi: 10.1021/jacs.8b12832. Epub 2019 Jan 14.
A novel enantioselective aminomethylation reaction of diazo compound, alcohol and α-aminomethyl ether enabled by asymmetric counteranion-directed catalysis is disclosed that offers an efficient and convenient access to furnish optically active α-hydroxyl-β-amino acids in high yield with high to excellent enantioselectivities. Control experiments and DFT calculations indicate that the transformation proceeds through trapping the in situ generated enol intermediate with methylene iminium ion, and the asymmetric induction was enabled by chiral pentacarboxycyclopentadiene anion via H-bonding and electrostatic interaction.
本文报道了一种新型的手性抗衡阴离子导向的不对称催化的重氮化合物、醇和α-氨甲基醚的对映选择性胺甲基化反应，为高效、方便地获得高对映选择性的光学活性α-羟基-β-氨基酸提供了一种新方法。控制实验和密度泛函理论计算表明，该转化是通过亚胺离子与原位生成的烯醇中间体的捕获来进行的，手性五羧基环戊二烯阴离子通过氢键和静电相互作用实现了不对称诱导。
