Artificial Metalloenzyme-Catalyzed Enantioselective Amidation via Nitrene Insertion in Unactivated C(sp 3)–H Bonds

Enantioselective C–H amidation offers attractive means to assemble C–N bonds to synthesize high-added value, nitrogen-containing molecules. In recent decades, complementary enzymatic and homogeneous-catalytic strategies for C–H amidation have been reported. Herein, we report on an artificial metallo...

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Published in:Journal of the American Chemical Society 2023-08, Vol.145 (30), p.16621-16629
Main Authors: Yu, Kun, Zou, Zhi, Igareta, Nico V., Tachibana, Ryo, Bechter, Julia, Köhler, Valentin, Chen, Dongping, Ward, Thomas R.
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cited_by cdi_FETCH-LOGICAL-a418t-5d6fa6b9bce05c2e964ecd5420ba6acede313597a1d555332d9fcbf8b052acf43
cites cdi_FETCH-LOGICAL-a418t-5d6fa6b9bce05c2e964ecd5420ba6acede313597a1d555332d9fcbf8b052acf43
container_end_page 16629
container_issue 30
container_start_page 16621
container_title Journal of the American Chemical Society
container_volume 145
creator Yu, Kun
Zou, Zhi
Igareta, Nico V.
Tachibana, Ryo
Bechter, Julia
Köhler, Valentin
Chen, Dongping
Ward, Thomas R.
description Enantioselective C–H amidation offers attractive means to assemble C–N bonds to synthesize high-added value, nitrogen-containing molecules. In recent decades, complementary enzymatic and homogeneous-catalytic strategies for C–H amidation have been reported. Herein, we report on an artificial metalloenzyme (ArM) resulting from anchoring a biotinylated Ir-complex within streptavidin (Sav). The resulting ArM catalyzes the enantioselective amidation of unactivated C­(sp 3)–H bonds. Chemogenetic optimization of the Ir cofactor and Sav led to significant improvement in both the activity and enantioselectivity. Up to >700 TON and 92% ee for the amidation of unactivated C­(sp 3)–H bonds was achieved. The single crystal X-ray analysis of the artificial nitrene insertase (ANIase) combined with quantum mechanics-molecular mechanics (QM-MM) calculations sheds light on critical second coordination sphere contacts leading to improved catalytic performance.
doi_str_mv 10.1021/jacs.3c03969
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title Artificial Metalloenzyme-Catalyzed Enantioselective Amidation via Nitrene Insertion in Unactivated C(sp 3)–H Bonds
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