Manganese terpyridine artificial metalloenzymes for benzylic oxygenation and olefin epoxidation

TETRAHEDRON

卷:70

Article

Zhang, Chen¹  Srivastava, Poonam¹  Ellis-Guardiola, Ken¹  Lewis, Jared C.¹ 

[1] Univ Chicago, Dept Chem, Chicago, IL 60637 USA

关键词: Artificial metalloenzyme;    Manganese;    C-H functionalization;    Epoxidation;    Biocatalysis;   

DOI  :  10.1016/j.tet.2014.03.008

来源: Elsevier

【 摘 要 】

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. (C) 2014 Elsevier Ltd. All rights reserved.

【 授权许可】

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