Department of Chemistry, University of Basel, Mattenstrasse 22, Basel CH-4058, Switzerland.
Department of Chemistry, University of Basel, Mattenstrasse 22, Basel CH-4058, Switzerland.
J Inorg Biochem. 2024 Sep;258:112621. doi: 10.1016/j.jinorgbio.2024.112621. Epub 2024 May 31.
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.
CH 功能化是现代有机化学中一个很有前途的领域，它可以促进惰性 CH 键向多种有价值的官能团的直接转化。尽管具有这些优点，但传统的均相催化在这种转化的效率、选择性和可持续性方面往往面临挑战。在这种情况下，人工金属酶（ArM）是通过将催化活性金属辅因子整合到可进化的蛋白质支架中而产生的，它在酶转化的效率和过渡金属催化的多功能性之间架起了桥梁。因此，ArM 已成为各种挑战性催化转化的有吸引力的工具。此外，定向进化的出现为优化酶催化开辟了前所未有的途径。利用其基因编码的蛋白质支架，ArM 已经被进化来催化各种 CH 功能化反应。本综述深入探讨了 ArM 催化的 CH 功能化反应的最新进展，强调了在宿主蛋白中围绕金属辅因子工程第二配位层的好处。
