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

Cascade approach to synthesize BIMs and analogues in different nucleophilic conditions DOI

Kailas Arjun Chavan,

Prakash N. Chavan,

Akhilesh Kumar

et al.

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 148, P. 155248 - 155248

Published: Aug. 11, 2024

Language: Английский

Citations

0
Acid–Solvent Cluster-Promoted General and Regioselective Friedel–Crafts Acylation with Carboxylic Acids DOI
Xi Wang,

Wanting Fu,

Yuan‐Li Ding

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 10, 2024

Carboxylic acids are considered to be the most ideal acylating reagents for Friedel-Crafts acylation. However, low electrophilicity of carboxylic and ability their byproduct water deactivate Lewis Brønsted greatly limit application in this reaction. In work, we developed a general regioselective acylation with acids, wherein unactivated/activated arenes various aromatic aliphatic were viable starting materials. Key accomplishment is use trifluoromethanesulfonic acid-hexafluoroisopropanol clusters.

Language: Английский

Citations

0
Expanding the scope of copper artificial metalloenzymes: A potential fluorinase? DOI Creative Commons

Isabeau Lüddecke,

Amanda G. Jarvis

Journal of Inorganic Biochemistry, Journal Year: 2024, Volume and Issue: 263, P. 112777 - 112777

Published: Nov. 19, 2024

Language: Английский

Citations

0
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

Citations

1
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

Citations

1