Enzymatic Friedel‐Crafts Alkylation Using Squalene‐Hopene Cyclases DOI Creative Commons

Sabrina Henche,

Bettina M. Nestl, Bernhard Hauer

et al.

ChemCatChem, Journal Year: 2021, Volume and Issue: 13(15), P. 3405 - 3409

Published: May 26, 2021

Abstract The Friedel‐Crafts alkylation constitutes one of the most important reactions for formation carbon‐carbon bonds. Here, we report using squalene‐hopene cyclases, which provides a biological alternative to traditional strategy. cyclase from Alicyclobacillus acidocaldarius ( Aac SHC) and variants have been demonstrated broad substrate reaction scope, making them valuable potential applications in biocatalysis. Notably, geranyl phenyl ether was found be highly regioselective. Furthermore, cyclases exhibit promiscuous activity catalyzing hydration an aqueous buffer. Finally, analyzed roles various active‐site residues studied their influence on product specificity. These findings highlight promise enzymatic catalysis enabling selective C−C bond formations.

Language: Английский

Recent advances in enzymatic carbon–carbon bond formation DOI Creative Commons
Hua Zhao

RSC Advances, Journal Year: 2024, Volume and Issue: 14(36), P. 25932 - 25974

Published: Jan. 1, 2024

Enzymatic carbon-carbon (C-C) bond formation reactions have become an effective and invaluable tool for designing new biological medicinal molecules, often with asymmetric features. This review provides a systematic overview of key C-C enzymes, the focus reaction mechanisms recent advances. These include aldol reaction, Henry Knoevenagel condensation, Michael addition, Friedel-Crafts alkylation acylation, Mannich Morita-Baylis-Hillman (MBH) Diels-Alder acyloin condensations

Language: Английский

Citations

2
Design and Evolution of an Artificial Friedel–Crafts Alkylation Enzyme Featuring an Organoboronic Acid Residue DOI

Shu‐Bin Mou,

Kai‐Yue Chen,

Thittaya Kunthic

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(39), P. 26676 - 26686

Published: Aug. 27, 2024

Creating artificial enzymes by the genetic incorporation of noncanonical amino acids with catalytic side chains would expand enzyme chemistries that have not been discovered in nature. Here, we report design an uses

Language: Английский

Citations

2
In Vivo Assembly of Artificial Metalloenzymes and Application in Whole‐Cell Biocatalysis** DOI Creative Commons
Shreyans Chordia, Siddarth Narasimhan, Alessandra Lucini Paioni

et al.

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 133(11), P. 5978 - 5985

Published: Jan. 15, 2021

Abstract We report the supramolecular assembly of artificial metalloenzymes (ArMs), based on Lactococcal multidrug resistance regulator (LmrR) and an exogeneous copper(II)–phenanthroline complex, in cytoplasm E. coli cells. A combination catalysis, cell‐fractionation, inhibitor experiments, supplemented with in‐cell solid‐state NMR spectroscopy, confirmed assembly. The ArM‐containing whole cells were active catalysis enantioselective Friedel–Crafts alkylation indoles Diels–Alder reaction azachalcone cyclopentadiene. Directed evolution resulted two different improved mutants for both reactions, LmrR_A92E_M8D LmrR_A92E_V15A, respectively. whole‐cell ArM system required no engineering microbial host, protein scaffold, or cofactor to achieve catalysis. consider this a key step towards integrating abiological biosynthesis generate hybrid metabolism.

Language: Английский

Citations

15
New Benchmark in DNA-Based Asymmetric Catalysis: Prevalence of Modified DNA/RNA Hybrid Systems DOI Creative Commons
Nicolas Duchemin, Sidonie Aubert, João Vicente Braga de Souza

et al.

JACS Au, Journal Year: 2022, Volume and Issue: 2(8), P. 1910 - 1917

Published: Aug. 2, 2022

By harnessing the chirality of DNA double helix, chemists have been able to obtain new, reliable, selective, and environmentally friendly biohybrid catalytic systems with tailor-made functions. Nonetheless, despite all advances made throughout years in field DNA-based asymmetric catalysis, many challenges still remain be faced, particular when it comes designing a "universal" catalyst broad reactivity unprecedented selectivity. Rational design rounds selection allowed us approach this goal. We report here development DNA/RNA hybrid system featuring covalently attached bipyridine ligand, which exhibits unmatched levels selectivity current toolbox opens new avenues catalysis.

Language: Английский

Citations

10
Enzymatic Friedel‐Crafts Alkylation Using Squalene‐Hopene Cyclases DOI Creative Commons

Sabrina Henche,

Bettina M. Nestl, Bernhard Hauer

et al.

ChemCatChem, Journal Year: 2021, Volume and Issue: 13(15), P. 3405 - 3409

Published: May 26, 2021

Abstract The Friedel‐Crafts alkylation constitutes one of the most important reactions for formation carbon‐carbon bonds. Here, we report using squalene‐hopene cyclases, which provides a biological alternative to traditional strategy. cyclase from Alicyclobacillus acidocaldarius ( Aac SHC) and variants have been demonstrated broad substrate reaction scope, making them valuable potential applications in biocatalysis. Notably, geranyl phenyl ether was found be highly regioselective. Furthermore, cyclases exhibit promiscuous activity catalyzing hydration an aqueous buffer. Finally, analyzed roles various active‐site residues studied their influence on product specificity. These findings highlight promise enzymatic catalysis enabling selective C−C bond formations.

Language: Английский

Citations

14