School of Chemistry, University of Manchester , Oxford Road, Manchester, M13 9PL, United Kingdom.
J Am Chem Soc. 2014 Nov 5;136(44):15775-80. doi: 10.1021/ja509236u. Epub 2014 Oct 21.
The reactivity of a rotaxane that acts as an aminocatalyst for the functionalization of carbonyl compounds through HOMO and LUMO activation pathways has been studied. Its catalytic activity is explored for C-C and C-S bond forming reactions through iminium catalysis, in nucleophilic substitutions and additions through enamine intermediates, in Diels-Alder reactions via trienamine catalysis, and in a tandem iminium-ion/enamine reaction. The catalyst can be switched "on" or "off", effectively controlling the rate of all of these chemical transformations, by the in situ change of the position of the macrocycle between two different binding sites on the rotaxane thread.
已研究了作为通过 HOMO 和 LUMO 激活途径对羰基化合物官能化的氨基催化剂的轮烷的反应性。 通过亚胺催化探索了其在 C-C 和 C-S 键形成反应、通过烯胺中间体在亲核取代和加成反应、通过三烯胺催化在 Diels-Alder 反应以及在亚胺离子/烯胺串联反应中的催化活性。 通过轮烷线在两个不同结合部位之间的大环的位置的原位变化，可以将催化剂“打开”或“关闭”，有效地控制所有这些化学反应的速率。
