Zhang Chen, Srivastava Poonam, Ellis-Guardiola Ken, Lewis Jared C
Department of Chemistry, University of Chicago, 5735 S. Ellis Ave., Chicago, IL 60637 (USA).
Tetrahedron. 2014 Jul 8;70(27-28):4245-4249. doi: 10.1016/j.tet.2014.03.008.
New catalysts for non-directed hydrocarbon functionalization have great potential in organic synthesis. We hypothesized that incorporating a Mn-terpyridine cofactor into a protein scaffold would lead to artificial metalloenzymes (ArMs) in which the selectivity of the Mn cofactor could be controlled by the protein scaffold. We designed and synthesized a maleimide-substituted Mn-terpyridine cofactor and demonstrated that this cofactor could be incorporated into two different scaffold proteins to generate the desired ArMs. The structure and reactivity of one of these ArMs was explored, and the broad oxygenation capability of the Mn-terpyridine catalyst was maintained, providing a robust platform for optimization of ArMs for selective hydrocarbon functionalization.
用于非定向烃官能化的新型催化剂在有机合成中具有巨大潜力。我们推测，将锰-三联吡啶辅因子整合到蛋白质支架中会产生人工金属酶（ArMs），其中锰辅因子的选择性可由蛋白质支架控制。我们设计并合成了一种马来酰亚胺取代的锰-三联吡啶辅因子，并证明该辅因子可整合到两种不同的支架蛋白中以生成所需的人工金属酶。对其中一种人工金属酶的结构和反应活性进行了探索，并且锰-三联吡啶催化剂的广泛氧化能力得以保持，为优化用于选择性烃官能化的人工金属酶提供了一个强大的平台。
