Biocatalytic Friedel‐Crafts Reactions
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TL;DR: This Review concludes with an overview of the frontiers of this field and routes towards more efficient and benign Friedel‐Crafts reactions for the future of humankind.
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Abstract: Friedel‐Crafts alkylation and acylation reactions are important methodologies in synthetic and industrial chemistry for the construction of aryl‐alkyl and aryl‐acyl linkages that are ubiquitous in bioactive molecules. Nature also exploits these reactions in many biosynthetic processes. Much work has been done to expand the synthetic application of these enzymes to unnatural substrates through directed evolution. The promise of such biocatalysts is their potential to supersede inefficient and toxic chemical approaches to these reactions, with mild operating conditions ‐ the hallmark of enzymes. Complementary work has created many bio‐hybrid Friedel‐Crafts catalysts consisting of chemical catalysts anchored into biomolecular scaffolds, which display many of the same desirable characteristics. In this Review, we summarise these efforts, focussing on both mechanistic aspects and synthetic considerations, concluding with an overview of the frontiers of this field and routes towards more efficient and benign Friedel‐Crafts reactions for the future of humankind.
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TL;DR: Friedel-Crafts reactions are key reactions in biomolecular chemistry, enabling alkylation and acylation of biomolecules.
5
Hierarchical Porous WO3@SiO2 Self-Standing Monolithic Catalysts and Their Efficient Cycling “Cosolvent-Free” Friedel–Crafts Alkylation/Acylation Catalytic Properties
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TL;DR: Researchers design hierarchical porous WO3@SiO2 monolithic catalysts with multiscale porosity, leveraging tungsten oxide's Brønsted-Lewis acidity for efficient cosolvent-free Friedel-Crafts alkylation and acylation reactions, achieving high turnover numbers and selectivity.
4
Biosynthesis of 4-Acyl-5-aminoimidazole Alkaloids Featuring a New Friedel-Crafts Acyltransferase.
Yuwei Xia,Guoliang Zhu,Xingwang Zhang,Sheng-Nan Li,Lei Du,Weiming Zhu +5 more
TL;DR: Biosynthesis of 4-acyl-5-aminoimidazole alkaloids featuring a new Friedel-Crafts acyltransferase involves the activation of fatty acyl groups, transfer onto the key residue Cys49 of SmzB, and subsequent C-C bond formation with 5-aminoimidazole ribonucleotide.
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References
Biocatalytic One-Pot Synthesis of l-Tyrosine Derivatives from Monosubstituted Benzenes, Pyruvate, and Ammonia
TL;DR: 3-methyl-l-tyrosine derivatives were obtained in >97% ee via a biocatalytic one-pot two-step cascade using substituted benzenes, pyruvate, and NH3 as starting materials.
61
Production of L-dihydroxyphenylalanine in Escherichia coli with the tyrosine phenol-lyase gene cloned from Erwinia herbicola.
TL;DR: The gene (tutA) encoding tyrosine phenol-lyase from Erwinia herbicola was cloned into Escherichia coli, and fusions to the lac and tac promoters were constructed to express the enzyme at high levels in E. coli.
60
Biocatalytic Friedel-Crafts Acylation and Fries Reaction.
TL;DR: A bacterial acyltransferase which can catalyze Friedel–Crafts C‐acylation of phenolic substrates in buffer without the need of CoA‐activated reagents is described, which opens an avenue for the development of alternative and selective C−C bond formation methods.
58
CouO and NovO: C-methyltransferases for tailoring the aminocoumarin scaffold in coumermycin and novobiocin antibiotic biosynthesis.
TL;DR: The specific timing of C-methylation in the aminocoumarin antibiotic pathways is established.
56
Enzymatic studies on aromatic prenyltransferases.
TL;DR: Several examples of the studies on chemoenzymatic synthesis of unnatural prenylated compounds and the enzyme engineering of ABBA-type and DMATS-type PTases are introduced.