PMID- 37471698
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20230807
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Print)
IS  - 0002-7863 (Linking)
VI  - 145
IP  - 30
DP  - 2023 Aug 2
TI  - Artificial Metalloenzyme-Catalyzed Enantioselective Amidation via Nitrene 
      Insertion in Unactivated C(sp(3))-H Bonds.
PG  - 16621-16629
LID - 10.1021/jacs.3c03969 [doi]
AB  - 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.
FAU - Yu, Kun
AU  - Yu K
AUID- ORCID: 0009-0007-3344-7553
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
FAU - Zou, Zhi
AU  - Zou Z
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
FAU - Igareta, Nico V
AU  - Igareta NV
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
FAU - Tachibana, Ryo
AU  - Tachibana R
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
FAU - Bechter, Julia
AU  - Bechter J
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
FAU - Kohler, Valentin
AU  - Kohler V
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
FAU - Chen, Dongping
AU  - Chen D
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
FAU - Ward, Thomas R
AU  - Ward TR
AUID- ORCID: 0000-0001-8602-5468
AD  - Department of Chemistry, University of Basel, Mattenstrasse 24a, BPR 1096, Basel 
      CH-4058, Switzerland.
LA  - eng
PT  - Journal Article
DEP - 20230720
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
SB  - IM
PMC - PMC10401721
COIS- The authors declare no competing financial interest.
EDAT- 2023/07/20 19:14
MHDA- 2023/07/20 19:15
PMCR- 2023/08/04
CRDT- 2023/07/20 16:13
PHST- 2023/07/20 19:15 [medline]
PHST- 2023/07/20 19:14 [pubmed]
PHST- 2023/07/20 16:13 [entrez]
PHST- 2023/08/04 00:00 [pmc-release]
AID - 10.1021/jacs.3c03969 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2023 Aug 2;145(30):16621-16629. doi: 10.1021/jacs.3c03969. Epub 
      2023 Jul 20.