Using BpyAla to generate Copper Artificial Metalloenzymes: a catalytic and structural study DOI Creative Commons
Eva Klemencic, Richard C. Brewster, Hafız Muhammad Ali

et al.

Published: Oct. 30, 2023

Artificial metalloenzymes (ArMs) have emerged as a promising avenue in the field of biocatalysis, offering new reactivity. However, their design remains challenging due to limited understanding protein dynamics and how introduced cofactors alter scaffold structure. Here we present structures catalytic activity novel copper ArMs capable (R)- or (S)-stereoselective control, utilizing steroid carrier (SCP) scaffold. To incorporate 2,2’-Bipyridine (Bpy) into SCP, two distinct strategies were employed: either Bpy was an unnatural amino acid (2,2’-bipyridin-5-yl)alanine (BpyAla) using amber stop codon expression via bioconjugation bromomethyl-Bpy cysteine residues. The resulting proved be effective at catalysing enantioselective Friedel-Crafts reaction with SCP_Q111BpyAla achieving best selectivity enantioselectivity 72% ee (S). Interestingly, despite same scaffold, different attachment for residue (Q111) led switch enantiopreference ArM.

Language: Английский

Hierarchical Porous WO3@SiO2 Self-Standing Monolithic Catalysts and Their Efficient Cycling “Cosolvent-Free” Friedel–Crafts Alkylation/Acylation Catalytic Properties DOI
Antoine Vardon,

Elodie Layan,

Frédéric Louërat

et al.

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(16), P. 6502 - 6516

Published: Aug. 7, 2023

Taking advantage of tungsten oxide inherent Brønsted–Lewis acidity, the first series WO3–SiO2(HIPE) monolithic (MUB-104(x) series) catalysts bearing multiscale porosity have been designed through integrative chemistry. At microscopic length scale, beyond X-ray diffraction (XRD) revealing WO3 monoclinic structure, local electron spin resonance (ESR) spectroscopy addresses g values clearly located at frontier between extended phases and polyanion clusters, in agreement with scanning transmission microscopy high-angle annular dark field (STEM-HAADF) investigations. NH3-TPD shows that when loading is increased from 10 wt % for MUB-104(1) to 24 MUB-104(3), amount acidic sites significantly decreases 0.35 0.08 mmol NH3 g–1, respectively, particle sizes. The MUB-104(x) offers efficient cosolvent-less heterogeneous cycling catalysis toward both Friedel–Crafts alkylation acylation syntheses. carries highest turnover number (TON) 121 frequency (TOF) 20 h–1, while acylation, TON 117 TOF 26 h–1. Besides, we find out offer good selectivity, where 30/70% ortho- para-substituted alkylated products are obtained. Considering reaction, selectivity even higher, reaching 100% acylated product. catalyst, due its intrinsic character, can be easily extracted reactive media, recycled, re-employed further.

Language: Английский

Citations

4
Catalytic Enantioselective Friedel-Crafts Allenylic Alkylation DOI Creative Commons
Priyotosh Das, Debangshu Ghosh, Santanu Mukherjee

et al.

Published: Nov. 9, 2023

The first catalytic enantioselective Friedel-Crafts (FC) allenylic alkylation for the creation of central chirality has been developed under cooperative Ir(I)/(phosphoramidite,olefin) and Lewis acid catalysis. Using racemic alcohol as electrophile, this enantioconvergent reaction proceeds through an Ir(I)-stabilized carbocation intermediate, which is intercepted with a variety electron-rich arenes heteroarenes. resulting highly enantioenriched (up to >99.5:0.5 er) 1,1-disubstituted methanes, bearing benzylic carbon stereocenter, are obtained complete regiocontrol – both on (hetero)arenes well fragment. This protocol allows formal introduction 4 alkane chains into stereocenter. An intramolecular version FC also shown proceed promising enantioselectivity same conditions.

Language: Английский

Citations

4
Friedel-Crafts Reactions for Biomolecular Chemistry DOI Creative Commons
Jun Ohata

Published: March 12, 2024

Chemical tools and principles have become central to biological medical research/applications by leveraging a range of classical organic chemistry reactions. Friedel-Crafts alkylation acylation are arguably one the most well-known used synthetic methods for preparation small molecules but its use in fields relatively less frequent than other reactions, possibly owing notion about plausible incompatibility with systems. This Review demonstrates advances reactions variety biomolecular fields. With discoveries applications numerous biomolecule-catalyzed or –assisted processes, garnered considerable interests biochemistry, enzymology, biocatalysis. Despite challenges reactivity selectivity demonstrated utility construction functionalization all four major biomolecules (i.e., nucleosides, carbohydrates/saccharides, lipids/fatty acids, amino acids/peptides/proteins), their diverse biological, medical, material discussed. As often fundamental educational components courses, is intended both experts nonexperts discussing basic reaction patterns (with depiction each mechanism Electronic Supplementary Information) relevant real-world impacts order enrich chemical research education. The significant growth described here testament broad importance utility, further development investigation will surely be focus

Language: Английский

Citations

1
Acid–solvent cluster-catalyzed general and regioselective Friedel–Crafts arylation of alcohols DOI

Wanting Fu,

Junkai Fu, Xi Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(13), P. 3602 - 3608

Published: Jan. 1, 2024

An acid–solvent clusters-catalyzed general and regioselective Friedel–Crafts alkylation has been described.

Language: Английский

Citations

1
Biosynthesis of 4-Acyl-5-aminoimidazole Alkaloids Featuring a New Friedel–Crafts Acyltransferase DOI
Yuwei Xia, Guoliang Zhu, Xingwang Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26308 - 26317

Published: Nov. 20, 2023

Friedel–Crafts acylation (FCA) is a highly beneficial approach in organic chemistry for creating the important C–C bonds that are necessary building intricate frameworks between aromatic substrates and an acyl group. However, there few reports about enzyme catalyzed FCA reactions. In this study, 4-acyl-5-aminoimidazole alkaloids (AAIAs), streptimidazoles A–C (1–3), enantiopure (+)-nocarimidazole C (4) as well their ribosides, streptimidazolesides A–D (5–8), were identified from fermentation broth of Streptomyces sp. OUCMDZ-944 or heterologous S. coelicolor M1154 mutant. The biosynthetic gene cluster (smz) was identified, pathway AAIAs elucidated first time. vivo vitro studies proved catalytic activity four essential genes smzB, -C, -E, -F biosynthesis clarified process alkaloids. ligase SmzE activates fatty groups connects them to carrier protein (ACP) holo-SmzF. Then, group transferred onto key residue Cys49 SmzB, new acyltransferase (FCase). Subsequently, reaction 5-aminoimidazole ribonucleotide (AIR) occurs generate intermediate AAIA-nucleotides by SmzB. Finally, hydrolase SmzC catalyzes N-glycosidic bond cleavage intermediates form AAIAs. Structural simulation, molecular modeling, mutational analysis SmzB showed Tyr26, Cys49, Tyr93 residues formation chain AAIAs, providing mechanistic insights into enzymatic reaction.

Language: Английский

Citations

3
Electrifying Friedel–Crafts Intramolecular Alkylation toward 1,1-Disubstituted Tetrahydronaphthalenes DOI Creative Commons
Enrico Lunghi,

Pietro Ronco,

Federico Della Negra

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(24), P. 16783 - 16789

Published: Nov. 30, 2023

In this work, we successfully employed electrochemical conditions to promote a Hofer-Moest, intramolecular Friedel-Crafts alkylation sequence. The reaction proceeds under mild conditions, employing carboxylic acids as starting materials. Notably, the process performed in batch was adapted continuous flow electrolysis apparatus provide significant improvement. This catalyst-free, approach produces an array of tetrahydronaphthalenes that could be used for API synthesis.

Language: Английский

Citations

3
“One-Pot” Construction of Networked AlCl3·6H2O@β-CD Composites by Mechanical Milling: A Green and Efficient Catalyst for the Synthesis of Bisindolylmethane Compounds DOI
Qiuping Zhang, Gang Wang, Xiang Li

et al.

Catalysis Letters, Journal Year: 2023, Volume and Issue: 154(1), P. 270 - 279

Published: Feb. 18, 2023

Language: Английский

Citations

2
Access to Substituted 1,1‐diarylalkanes by Friedel‐Crafts Benzylations Mediated by FeCl3‐based Deep Eutectic Solvents DOI Creative Commons
Marina Ramos‐Martín, Joaquín García‐Álvarez, Alejandro Presa Soto

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 25, 2024

Abstract The development of new, more efficient Friedel–Crafts benzylation methodologies that provide access to 1,1‐diarylalkanes is an important objective interest for the production pharmaceuticals and fine chemical products. In this regard, study introduces a novel synthetic route conducted in Deep Eutectic Solvent ( DES ) 3 FeCl ⋅ 6 H 2 O/ Gly , which serves as both reaction medium promoter. Under these conditions, benzylations various arenes bearing activating deactivating ortho ‐/ para ‐directing groups, can be performed using diverse benzylating reagents such styrenes, alcohols, acetates, ethers, chlorides. Importantly, highly electronically deactivated electrophiles, including those with CF NO are suitable substrates. This methodology provides wide range asymmetric (up 132 examples) generally good yields high regioselectivities. efficiency approach was demonstrated multigram‐scale synthesis (10 mmol) 1‐phenyl‐1‐xylyl ethane PXE ), liquid great industrial applicability. Moreover, Fe(III)‐based could reused 20 consecutive cycles no appreciable erosion yields.

Language: Английский

Citations

0
Catalytic Enantioselective Friedel‐Crafts Allenylation DOI
Priyotosh Das, Debangshu Ghosh, Santanu Mukherjee

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 7, 2024

Abstract The first enantioselective Friedel‐Crafts (FC) allenylation reaction for the creation of central chirality is developed under cooperative Ir(I)/(phosphoramidite,olefin) and Lewis acid catalysis. This enantioconvergent utilizes racemic allenylic alcohol as electrophile shows compatibility with a variety electron‐rich arenes heteroarenes. resulting highly enantioenriched (up to >99.5 : 0.5 e.r.) 1,1‐disubstituted methanes, bearing benzylic carbon stereocenter, are obtained complete regiocontrol – both on (hetero)arenes well fragment. protocol allows formal introduction 4‐carbon alkyl chain into (hetero)arenes, along stereocenter. Judicious synthetic elaborations not only lead FC alkylation products less but also substituted in ortho ‐ even meta ‐selective fashion. An intramolecular version this shown proceed promising enantioselectivity same catalytic conditions. Mechanistic studies revealed involvement dynamic kinetic asymmetric transformation (DyKAT) alcohols reaction.

Language: Английский

Citations

0
Catalytic Enantioselective Friedel‐Crafts Allenylation DOI Open Access
Priyotosh Das, Debangshu Ghosh, Santanu Mukherjee

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(47)

Published: Aug. 7, 2024

Abstract The first enantioselective Friedel‐Crafts (FC) allenylation reaction for the creation of central chirality is developed under cooperative Ir(I)/(phosphoramidite,olefin) and Lewis acid catalysis. This enantioconvergent utilizes racemic allenylic alcohol as electrophile shows compatibility with a variety electron‐rich arenes heteroarenes. resulting highly enantioenriched (up to >99.5 : 0.5 e.r.) 1,1‐disubstituted methanes, bearing benzylic carbon stereocenter, are obtained complete regiocontrol – both on (hetero)arenes well fragment. protocol allows formal introduction 4‐carbon alkyl chain into (hetero)arenes, along stereocenter. Judicious synthetic elaborations not only lead FC alkylation products less but also substituted in ortho ‐ even meta ‐selective fashion. An intramolecular version this shown proceed promising enantioselectivity same catalytic conditions. Mechanistic studies revealed involvement dynamic kinetic asymmetric transformation (DyKAT) alcohols reaction.

Language: Английский

Citations

0