Enzymatic catalysis is largely based on intramolecular cooperativity between a metal center and functional organic molecules located on one scaffold. Inspired by this concept we have designed the metallopeptoid trimer BT, which is a unique intramolecular cooperative oxidation catalyst incorporating two catalytic centers, phenanthroline-copper and TEMPO, as well as one non-catalytic benzyl group. Herein we explore the capability of BT to act as an efficient catalyst for the oxidative synthesis of imines, which are versatile intermediates in the fine chemicals and pharmaceutical industries. We demonstrate that BT, combined with CuI, can catalyze the production of benzyl, aryl, heteroaryl, allylic and aliphatic imines from various alcohols and amines with a turn-over-number up to 45 times higher than this achieved when phenanthroline, copper and TEMPO are mixed in solution. Moreover, in low catalyst(s) loading, BT enables transformations that are not possible when a mixture of the individual catalysts is employed.

酶催化主要基于金属中心与位于一个支架上的功能性有机分子之间的分子内合作性。受此概念的启发，我们设计了类金属三聚体BT，这是一种独特的分子内协同氧化催化剂，结合了两个催化中心，菲咯啉-铜和TEMPO，以及一个非催化苄基。本文中，我们探讨了BT充当亚胺氧化合成的有效催化剂的能力，亚胺是精细化工和制药行业中的通用中间体。我们证明了英国电信与CuI结合使用，可以催化各种醇和胺生成苄基，芳基，杂芳基，烯丙基和脂族亚胺，其转换数比溶液中邻菲咯啉，铜和TEMPO混合时的转换数高45倍。 。此外，在低催化剂负载量下，BT使转化成为可能，当使用单独的催化剂的混合物时，这些转化是不可能的。