Aerobic Oxysulfonylation of Olefins Using N-Sulfonylaminophthalimides as Sulfonyl Radical Precursors DOI
Zhenxing Yan,

Ye Jie,

Heng Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6647 - 6651

Published: July 29, 2024

Readily accessible N-sulfonylaminophthalimides were developed to be efficient sulfonyl radical precursors upon being treated with a base/oxidant under mild conditions. The method was applied the oxysulfonylation of olefins, providing β-ketosulfones and isobenzofurans stereoselectively. On basis control experiments, density functional theory calculations, literature, plausible mechanism proposed. findings offered chance develop novel based on diversely substituted N-aminophthalimides, which might establish universal approach for generation various radicals.

Language: Английский

Asymmetric photoenzymatic incorporation of fluorinated motifs into olefins DOI
Mao‐Lin Li, Yaru Yuan, Wesley Harrison

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6707), P. 416 - 421

Published: July 25, 2024

Enzymes capable of assimilating fluorinated feedstocks are scarce. This situation poses a challenge for the biosynthesis compounds used in pharmaceuticals, agrochemicals, and materials. We developed photoenzymatic hydrofluoroalkylation that integrates motifs into olefins. The photoinduced promiscuity flavin-dependent ene-reductases enables generation carbon-centered radicals from iodinated fluoroalkanes, which directed by photoenzyme to engage enantioselectively with approach facilitates stereocontrol through interaction between singular unit enzyme, securing high enantioselectivity at β, γ, or δ positions groups enzymatic hydrogen atom transfer-a process is notably challenging conventional chemocatalysis. work advances strategies integrating chemical opens avenues asymmetric synthesis compounds.

Language: Английский

Citations

16
Modular Access to Chiral Amines via Imine Reductase-Based Photoenzymatic Catalysis DOI
Bin Chen, Renjie Li, Jianqiang Feng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 14278 - 14286

Published: May 10, 2024

The development of catalysts serves as the cornerstone innovation in synthesis, exemplified by recent discovery photoenzymes. However, repertoire naturally occurring enzymes repurposed direct light excitation to catalyze new-to-nature photobiotransformations is currently limited flavoproteins and keto-reductases. Herein, we shed on imine reductases (IREDs) that remote C(sp3)–C(sp3) bond formation, providing a previously elusive radical hydroalkylation enamides for accessing chiral amines (45 examples with up 99% enantiomeric excess). Beyond their natural function catalyzing two-electron reductive amination reactions, upon visible-light or synergy synthetic photoredox catalyst, IREDs are tune non-natural photoinduced single-electron processes. By conducting wet mechanistic experiments computational simulations, unravel how engineered intermediates toward productive enantioselective pathway. This work represents promising paradigm harnessing nature's asymmetric transformations remain challenging through traditional chemocatalytic methods.

Language: Английский

Citations

7
Threonine Aldolase-Catalyzed Enantioselective α-Alkylation of Amino Acids through Unconventional Photoinduced Radical Initiation DOI

Tian-Ci Wang,

Zheng Zhang, Guodong Rao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22476 - 22484

Published: July 4, 2024

Visible light-driven pyridoxal radical biocatalysis has emerged as a promising strategy for the stereoselective synthesis of valuable noncanonical amino acids (ncAAs). Previously, use well-tailored photoredox catalysts represented key to enable efficient phosphate (PLP) enzyme-catalyzed reactions. Here, we report PLP-dependent threonine aldolase-catalyzed asymmetric α-C–H alkylation abundant using Katritzky pyridinium salts alkylating agents. The engineered aldolases allowed this redox-neutral proceed efficiently, giving rise challenging α-trisubstituted and -tetrasubstituted ncAA products in protecting-group-free fashion with excellent enantiocontrol. Mechanistically, enantioselective α-alkylation capitalizes on unique reactivity persistent enzymatic quinonoid intermediate derived from PLP cofactor acid substrate allow novel C–C coupling. Surprisingly, photobiocatalytic process does not require well-established operates through an unconventional photoinduced generation involving PLP-derived aldimine. ability develop reactions without relying classic photocatalysts or photoenzymes opens up new avenues advancing intermolecular that are known either organic chemistry enzymology.

Language: Английский

Citations

7
Enantioselective biosynthesis of vicinal diamines enabled by synergistic photo/biocatalysis consisting of an ene-reductase and a green-light-excited organic dye DOI

Fengming Shi,

Bin Chen, Jinhai Yu

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2025, Volume and Issue: 68, P. 223 - 229

Published: Jan. 1, 2025

Language: Английский

Citations

0
Mechanistic investigation of repurposed photoenzymes with new-to-nature reactivity DOI
Zhengyi Zhang, Mao‐Lin Li, Huimin Zhao

et al.

Current Opinion in Green and Sustainable Chemistry, Journal Year: 2025, Volume and Issue: 52, P. 101009 - 101009

Published: Feb. 27, 2025

Language: Английский

Citations

0
Repurposing Visible‐Light‐Excited Ene‐Reductases for Diastereo‐ and Enantioselective Lactones Synthesis DOI
Jinhai Yu, Qiaoyu Zhang, Beibei Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 24, 2024

Abstract Repurposing enzymes to catalyze non‐natural asymmetric transformations that are difficult achieve using traditional chemical methods is of significant importance. Although radical C−O bond formation has emerged as a powerful approach for constructing oxygen‐containing compounds, controlling the stereochemistry poses great challenge. Here we present development dual bio‐/photo‐catalytic system comprising an ene‐reductase and organic dye achieving stereoselective lactonizations. By integrating directed evolution photoinduced single electron oxidation, repurposed engineered ene‐reductases steer formations (one hydrolactonizations lactonization‐alkylations while two bonds lactonization‐oxygenations). This catalysis gave new diverse array enantioenhanced 5‐ 6‐membered lactones with vicinal stereocenters, part which bears quaternary stereocenter (up 99 % enantiomeric excess, up 12.9 : 1 diastereomeric ratio). Detailed mechanistic studies, including computational simulations, uncovered synergistic effect enzyme externally added organophotoredox catalyst Rh6G.

Language: Английский

Citations

3
Repurposing Visible‐Light‐Excited Ene‐Reductases for Diastereo‐ and Enantioselective Lactones Synthesis DOI
Jinhai Yu, Qiaoyu Zhang, Beibei Zhao

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(27)

Published: April 24, 2024

Abstract Repurposing enzymes to catalyze non‐natural asymmetric transformations that are difficult achieve using traditional chemical methods is of significant importance. Although radical C−O bond formation has emerged as a powerful approach for constructing oxygen‐containing compounds, controlling the stereochemistry poses great challenge. Here we present development dual bio‐/photo‐catalytic system comprising an ene‐reductase and organic dye achieving stereoselective lactonizations. By integrating directed evolution photoinduced single electron oxidation, repurposed engineered ene‐reductases steer formations (one hydrolactonizations lactonization‐alkylations while two bonds lactonization‐oxygenations). This catalysis gave new diverse array enantioenhanced 5‐ 6‐membered lactones with vicinal stereocenters, part which bears quaternary stereocenter (up 99 % enantiomeric excess, up 12.9 : 1 diastereomeric ratio). Detailed mechanistic studies, including computational simulations, uncovered synergistic effect enzyme externally added organophotoredox catalyst Rh6G.

Language: Английский

Citations

2
Chiral Sulfones via Single-Electron Oxidation-Initiated Photoenzymatic Catalysis DOI
Juntao Ye, Pandaram Sakthivel,

Qinglong Shi

et al.

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

Published: June 18, 2024

Abstract We recently achieved an oxidation-initiated photoenzymatic enantioselective hydrosulfonylation of olefins through the utilization a new Gluconobacter ene-reductase mutant (GluER-W100F-W342F). Our method simplifies reaction system by eliminating need for cofactor regeneration mixture and, in contrast with previous systems, does not depend on formation electron donor–acceptor (EDA) complex between substrates and enzyme cofactor. Moreover, GluER variant exhibits good substrate compatibility excellent enantioselectivity. Mechanistic investigations indicate that tyrosine-mediated HAT process is involved support proposed mechanism. In this Synpacts article, we discuss conceptual framework led to discovery reflect key aspects its development. 1 Introduction 2 Conceptual Background 2.1 Intramolecular Photoenzymatic Reactions via Single-Electron Reduction 2.2 Intermolecular 3 The Development Process 4 Conclusion

Language: Английский

Citations

0
Aerobic Oxysulfonylation of Olefins Using N-Sulfonylaminophthalimides as Sulfonyl Radical Precursors DOI
Zhenxing Yan,

Ye Jie,

Heng Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6647 - 6651

Published: July 29, 2024

Readily accessible N-sulfonylaminophthalimides were developed to be efficient sulfonyl radical precursors upon being treated with a base/oxidant under mild conditions. The method was applied the oxysulfonylation of olefins, providing β-ketosulfones and isobenzofurans stereoselectively. On basis control experiments, density functional theory calculations, literature, plausible mechanism proposed. findings offered chance develop novel based on diversely substituted N-aminophthalimides, which might establish universal approach for generation various radicals.

Language: Английский

Citations

0