Photoenzymatic Hydrosulfonylation for the Stereoselective Synthesis of Chiral Sulfones DOI
Xiaoyang Chen,

Dannan Zheng,

Linye Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 5, 2023

Abstract Chiral sulfones are recurrent motifs in pharmaceuticals and bioactive molecules. Although chemical methods have been developed to afford α‐ or β‐ chiral sulfones, these protocols rely heavily on the pre‐synthesis of structurally complicated starting materials metal complexes. Herein, we described a photoenzymatic approach for radical‐mediated stereoselective hydrosulfonylation. Engineered variants ene reductases provide efficient biocatalysts this transformation, enabling achieve series β‐chiral sulfonyl compounds with high yields (up 92 %) excellent e.r. values 99 : 1).

Language: Английский

Enzymatic strategies for asymmetric synthesis DOI Creative Commons
Mélanie Hall

RSC Chemical Biology, Journal Year: 2021, Volume and Issue: 2(4), P. 958 - 989

Published: Jan. 1, 2021

Asymmetric synthesis achieved with enzymes for stereoselective reduction and bond forming reactions, enantioselective atroposelective reactions.

Language: Английский

Citations

66
Ene‐Reductase: A Multifaceted Biocatalyst in Organic Synthesis DOI

Triptesh Kumar Roy,

Ramdas Sreedharan, Pintu Ghosh

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(21)

Published: Feb. 8, 2022

Abstract Biocatalysis integrate microbiologists, enzymologists, and organic chemists to access the repertoire of pharmaceutical agrochemicals with high chemoselectivity, regioselectivity, enantioselectivity. The saturation carbon‐carbon double bonds by biocatalysts challenges conventional chemical methodology as it bypasses use precious metals (in combination chiral ligands molecular hydrogen) or organocatalysts. In this line, Ene‐reductases (ERs) from Old Yellow Enzymes (OYEs) family are found be a prominent asymmetric biocatalyst that is increasingly used in academia industries towards unparalleled stereoselective trans ‐hydrogenations activated C=C bonds. ERs gained prominence they were individual catalysts, multi‐enzyme cascades, conjugation reagents (chemoenzymatic approach). Besides, ERs’ participation photoelectrochemical radical‐mediated process helps unlock many scopes outside traditional biocatalysis. These up‐and‐coming methodologies entice enzymologists explore, expand harness chemistries displayed for industrial settings. Herein, we reviewed last five year's exploration transformations using ERs.

Language: Английский

Citations

61
Recent Advances in Photobiocatalysis for Selective Organic Synthesis DOI

Yongzhen Peng,

Zhichun Chen, Jian Xu

et al.

Organic Process Research & Development, Journal Year: 2022, Volume and Issue: 26(7), P. 1900 - 1913

Published: Feb. 2, 2022

Photocatalysis has emerged as a powerful tool to generate reactive intermediates under mild reaction conditions. The combination of photocatalysis and biocatalysis, possessing advantages the reactivity photocatalysts selectivity enzymes, received increasing attention for its potential realize green synthesis value-added chemicals. This review provides an overview recent progress in photobiocatalysis, including regeneration cofactors, generation H2O2 situ, cascades involving photobiocatalytic transformation, photoinduced enzymatic reactions inspired by photoactive cofactor within enzyme.

Language: Английский

Citations

46
Asymmetric C-Alkylation of Nitroalkanes via Enzymatic Photoredox Catalysis DOI
Haigen Fu,

Tianzhang Qiao,

J. M. Carceller

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(2), P. 787 - 793

Published: Jan. 6, 2023

Tertiary nitroalkanes and the corresponding α-tertiary amines represent important motifs in bioactive molecules natural products. The C-alkylation of secondary with electrophiles is a straightforward strategy for constructing tertiary nitroalkanes; however, controlling stereoselectivity this type reaction remains challenging. Here, we report highly chemo- stereoselective alkyl halides catalyzed by an engineered flavin-dependent "ene"-reductase (ERED). Directed evolution old yellow enzyme from Geobacillus kaustophilus provided triple mutant, GkOYE-G7, capable synthesizing high yield enantioselectivity. Mechanistic studies indicate that excitation enzyme-templated charge-transfer complex formed between substrates cofactor responsible radical initiation. Moreover, single-enzyme two-mechanism cascade was developed to prepare simple nitroalkenes, highlighting potential use one two mechanistically distinct reactions.

Language: Английский

Citations

40
Photoenzymatic Hydrosulfonylation for the Stereoselective Synthesis of Chiral Sulfones DOI
Xiaoyang Chen,

Dannan Zheng,

Linye Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 5, 2023

Abstract Chiral sulfones are recurrent motifs in pharmaceuticals and bioactive molecules. Although chemical methods have been developed to afford α‐ or β‐ chiral sulfones, these protocols rely heavily on the pre‐synthesis of structurally complicated starting materials metal complexes. Herein, we described a photoenzymatic approach for radical‐mediated stereoselective hydrosulfonylation. Engineered variants ene reductases provide efficient biocatalysts this transformation, enabling achieve series β‐chiral sulfonyl compounds with high yields (up 92 %) excellent e.r. values 99 : 1).

Language: Английский

Citations

37