It is desired to design and construct more efficient enzymes with better performance to catalyze carbene N-H insertions for the synthesis of bioactive molecules. To this end, we exploited and designed a series of human neuroglobin (Ngb) mutants. As shown in this study, a double mutant, A15C/H64G Ngb, with an additional disulfide bond and a modified heme active site, exhibited yields up to >99% and total turnover numbers up to 33000 in catalyzing the carbene N-H insertions for aromatic amine derivatives, including those with a large size such as 1-aminopyrene. Moreover, for -phenylenediamine derivatives, they underwent two cycles of N-H insertions, followed by cyclization to form quinoxalinones, as confirmed by the X-ray crystal structures. This study suggests that Ngb can be designed into a functional carbene transferase for efficiently catalyzing carbene N-H insertion reactions with a range of substrates. It also represents the first example of the formation of quinoxalinones catalyzed by an engineered heme enzyme.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.3c02855 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
ML nanospheres as supramolecular templates for the controlled synthesis of Ir-nanoclusters and their use in the chemo-selective hydrogenation of nitro styrene.
Chem Sci
December 2024
Van't Hoff Institute for Molecular Sciences, University of Amsterdam 1098 XH Amsterdam The Netherlands
Article Synopsis
- * Researchers used a technique involving sulfonate functionalized N-heterocyclic carbene (NHC) Ir complexes and a special structural framework called a G-sphere to create these nanoclusters through hydrogen reduction.
- * The resulting nanoclusters (1.8 ± 0.4 nm) exhibited a narrow size distribution and were highly effective as catalysts for hydrogenating 4-nitrostyrene, showcasing superior selectivity compared to larger, non-encapsulated Ir clusters.
Rhodium-Catalyzed One-pot Chemoselective Insertion-Rearrangement-Cyclization of Azavinyl Carbenes with 2-Aminobenzyl Alcohols.
J Org Chem
November 2024
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
Chemoselective insertion of in situ generated α-imino rhodium carbene onto the O-H bond of 2-aminobenzyl alcohols over the N-H bond followed by [1,3]-alky shift has been successfully accomplished for the synthesis of amine tethered ketone derivatives. The resultant product was further cyclized under acidic conditions to afford biologically important 3-aminoquinolines. Successful integration of chemoselective insertion--rearrangement and cyclization in one pot offered access to various 3-aminoquinolines in a good yield.
View Article and Find Full Text PDFMechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X-H and C(sp)-H bonds.
Chem Soc Rev
November 2024
Department of Organic Chemistry, Indian Institute of Science, Bengaluru-560012, Karnataka, India.
Constructing highly proficient C-X (X = O, N, S, ) and C-C bonds by leveraging TMs (transition metals) (Fe, Cu, Pd, Rh, Au, ) and enzymes to catalyze carbene insertion into X-H/C(sp)-H is a highly versatile strategy. This is primarily achieved through the generation of metal carbenes from the interaction of TMs with diazo compounds. Over the last few decades, significant advancements have been made, encompassing a wide array of X-H bond insertions using various TMs.
View Article and Find Full Text PDFVisible-Light-Promoted N-H Insertion/Controllable Transformation of Diazoalkanes and 3-Aminomethylated Maleimides.
J Org Chem
September 2024
Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials and Key Laboratory of Functional Inorganic Materials of Anhui Province, College of Chemistry & Chemical Engineering, Anhui University, Hefei, Anhui 230601, People's Republic of China.
The utilization of photogenerated carbene species to perform N-H insertion reactions has attracted considerable attention in the past few years. In this Article, we disclose a visible-light-promoted N-H insertion of 3-aminomethylated maleimides with aryl diazoacetates under sole blue LED irradiation. Continuous flow reactor technology was exploited to improve the reaction efficiency.
View Article and Find Full Text PDFTransition Metal Parent Alumylene Complexes: Synthesis, Structures, and XPS Characterization of Aluminum Oxidation State.
Inorg Chem
September 2024
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Article Synopsis
- The first successful isolation and characterization of transition metal complexes featuring the Al(I)-H unit were carried out, resulting in W and Fe complexes with yields of 43-63%.
- The synthesis was achieved through a one-step reaction involving specific precursors and was characterized using various techniques, including NMR and IR spectroscopy, as well as DFT calculations.
- Additionally, the strong σ-donating property of the :AlH(NHC) ligand and the positively polarized coordination bonds were confirmed, alongside the validation of the Aluminum's monovalent oxidation state through X-ray photoelectron spectroscopy.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!