Abstract：
CH functionalization, a promising frontier in modern organic chemistry, facilitates the direct conversion of inert CH bonds into many valuable functional groups. Despite its merits, traditional homogeneous catalysis, often faces challenges in efficiency, selectivity, and sustainability towards this transformation. In this context, artificial metalloenzymes (ArMs), resulting from the incorporation of a catalytically-competent metal cofactor within an evolvable protein scaffold, bridges the gap between the efficiency of enzymatic transformations and the versatility of transition metal catalysis. Accordingly, ArMs have emerged as attractive tools for various challenging catalytic transformations. Additionally, the coming of age of directed evolution has unlocked unprecedented avenues for optimizing enzymatic catalysis. Taking advantage of their genetically-encoded protein scaffold, ArMs have been evolved to catalyze various CH functionalization reactions. This review delves into the recent developments of ArM-catalyzed CH functionalization reactions, highlighting the benefits of engineering the second coordination sphere around a metal cofactor within a host protein.
摘要：
CH功能化，现代有机化学的前沿,促进惰性CH键直接转化为许多有价值的官能团。尽管有其优点,传统的均相催化，经常面临效率方面的挑战，选择性,以及这种转变的可持续性。在这种情况下，人工金属酶（ArM），由于在可进化的蛋白质支架中掺入了催化能力的金属辅因子，弥合了酶促转化效率和过渡金属催化多功能性之间的差距。因此，Arm已成为各种具有挑战性的催化转化的有吸引力的工具。此外,定向进化时代的到来为优化酶催化打开了前所未有的途径。利用他们的基因编码的蛋白质支架，Arm已经发展成催化各种CH官能化反应。本文综述了ArM催化CH官能化反应的最新进展，突出了在宿主蛋白质内的金属辅因子周围工程化第二配位球的好处。
