Synergistic catalysis is a powerful tool that involves two or more distinctive catalytic systems to activate reaction partners simultaneously, thereby expanding the reactivity space of individual catalysis. As an established catalytic strategy, organocatalysis has found numerous applications in enantioselective transformations under rather mild conditions. Recently, the introduction of other catalytic systems has significantly expanded the reaction space of typical organocatalysis. In this regard, aminocatalysis is a prototypical example of synergistic catalysis. The combination of aminocatalyst and transition metal could be traced back to the early days of organocatalysis and has now been well explored as an enabling catalytic strategy. Particularly, the acid–base properties of aminocatalysis can be significantly expanded to include usually electrophiles generated in situ via metal-catalyzed cycles. Later on, aminocatalyst has also been exploited in synergistically combining with photochemical and electrochemical processes to facilitate redox transformations. However, synergistically combining one type of aminocatalyst with many different catalytic systems remains a great challenge. One of the most daunting challenges is the compatibility of aminocatalysts in coexistence with other catalytic species. As nucleophilic species, aminocatalysts may also bind with metal, which leads to mutual inhibition or even quenching of the individual catalytic activity. In addition, oxidative stability of aminocatalyst is also a non-neglectable issue, which causes difficulties in exploring oxidative enamine transformations.

中文翻译：

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手性伯胺“1+x”协同催化的对映选择性转化


协同催化是一种强大的工具，涉及两个或多个独特的催化系统来同时激活反应伙伴，从而扩大单个催化的反应空间。作为一种既定的催化策略，有机催化在相当温和的条件下在对映选择性转化中得到了广泛的应用。近年来，其他催化体系的引入显着扩大了典型有机催化的反应空间。在这方面，氨基催化是协同催化的典型例子。氨基催化剂和过渡金属的结合可以追溯到有机催化的早期，并且现在已经作为一种可行的催化策略得到了很好的探索。特别是，氨基催化的酸碱性质可以显着扩展，通常包括通过金属催化循环原位产生的亲电子试剂。后来，氨基催化剂也被用于与光化学和电化学过程协同结合以促进氧化还原转化。然而，将一种类型的氨基催化剂与许多不同的催化系统协同结合仍然是一个巨大的挑战。最艰巨的挑战之一是氨基催化剂与其他催化物种共存的相容性。作为亲核物质，氨基催化剂也可以与金属结合，从而导致相互抑制甚至猝灭单个催化活性。此外，氨基催化剂的氧化稳定性也是一个不可忽视的问题，这给探索氧化烯胺转化带来了困难。