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

Tianzhang Qiao,

J. M. Carceller

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(2), С. 787 - 793

Опубликована: Янв. 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.

Язык: Английский

Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds DOI
Yuan He, Zilong Huang, Kaikai Wu

и другие.

Chemical Society Reviews, Год журнала: 2022, Номер 51(7), С. 2759 - 2852

Опубликована: Янв. 1, 2022

C-H functionalization has been emerging as a powerful method to establish carbon-carbon and carbon-heteroatom bonds. Many efforts have devoted transition-metal-catalyzed direct transformations of Metal carbenes generated in situ from transition-metal compounds diazo or its equivalents are usually applied the transient reactive intermediates furnish catalytic cycle for new C-C C-X bond formation. Using this strategy unactivated simple alkanes complex molecules can be further functionalized transformed multi-functionalized compounds. In area, carbene insertion bonds paid continuous attention. Diverse catalyst design strategies, synthetic methods, potential applications developed. This critical review will summarize advance dated up July 2021, by categories aliphatic C(sp3)-H, aryl (aromatic) C(sp2)-H, heteroaryl (heteroaromatic) C(sp2)-H bonds, alkenyl alkynyl C(sp)-H, well asymmetric more coverage given recent work. Due rapid development future directions topic also discussed. give authors an overview chemistry with focus on systems

Язык: Английский

Процитировано

236

From nature to industry: Harnessing enzymes for biocatalysis DOI
Rebecca Buller, Stefan Lutz, Romas J. Kazlauskas

и другие.

Science, Год журнала: 2023, Номер 382(6673)

Опубликована: Ноя. 23, 2023

Biocatalysis harnesses enzymes to make valuable products. This green technology is used in countless applications from bench scale industrial production and allows practitioners access complex organic molecules, often with fewer synthetic steps reduced waste. The last decade has seen an explosion the development of experimental computational tools tailor enzymatic properties, equipping enzyme engineers ability create biocatalysts that perform reactions not present nature. By using (chemo)-enzymatic synthesis routes or orchestrating intricate cascades, scientists can synthesize elaborate targets ranging DNA pharmaceuticals starch made vitro CO2-derived methanol. In addition, new chemistries have emerged through combination biocatalysis transition metal catalysis, photocatalysis, electrocatalysis. review highlights recent key developments, identifies current limitations, provides a future prospect for this rapidly developing technology.

Язык: Английский

Процитировано

224

The E factor at 30: a passion for pollution prevention DOI Creative Commons
Roger A. Sheldon

Green Chemistry, Год журнала: 2023, Номер 25(5), С. 1704 - 1728

Опубликована: Янв. 1, 2023

Publication of the E Factor drew attention to problem waste in chemicals manufacture. Thirty yeas later it is abundantly clear that underlying cause global environmental problems, from climate change plastic pollution.

Язык: Английский

Процитировано

150

Stereodivergent atom-transfer radical cyclization by engineered cytochromes P450 DOI
Qi Zhou, M. A. Chin, Yue Fu

и другие.

Science, Год журнала: 2021, Номер 374(6575), С. 1612 - 1616

Опубликована: Дек. 23, 2021

Naturally occurring enzymes can be a source of unnatural reactivity that molded by directed evolution to generate efficient biocatalysts with valuable activities. Owing the lack exploitable stereocontrol elements in synthetic systems, steering absolute and relative stereochemistry free-radical processes is notoriously difficult asymmetric catalysis. Inspired innate redox properties first-row transition-metal cofactors, we repurposed cytochromes P450 catalyze stereoselective atom-transfer radical cyclization. A set metalloenzymes was engineered impose substantial over addition step halogen rebound these processes, allowing enantio- diastereodivergent This evolvable metalloenzyme platform represents promising solution tame fleeting intermediates for

Язык: Английский

Процитировано

139

Combining chemistry and protein engineering for new-to-nature biocatalysis DOI Open Access
David C. Miller, Soumitra V. Athavale, Frances H. Arnold

и другие.

Nature Synthesis, Год журнала: 2022, Номер 1(1), С. 18 - 23

Опубликована: Янв. 12, 2022

Язык: Английский

Процитировано

137

Designing Artificial Metalloenzymes by Tuning of the Environment beyond the Primary Coordination Sphere DOI
Casey Van Stappen, Yunling Deng, Yiwei Liu

и другие.

Chemical Reviews, Год журнала: 2022, Номер 122(14), С. 11974 - 12045

Опубликована: Июль 11, 2022

Metalloenzymes catalyze a variety of reactions using limited number natural amino acids and metallocofactors. Therefore, the environment beyond primary coordination sphere must play an important role in both conferring tuning their phenomenal catalytic properties, enabling active sites with otherwise similar environments to perform diverse array biological functions. However, since interactions are numerous weak, it has been difficult pinpoint structural features responsible for activities native enzymes. Designing artificial metalloenzymes (ArMs) offers excellent basis elucidate roles these further develop practical catalysts. In this review, we highlight how secondary spheres ArMs influence metal binding catalysis, particular focus on use protein scaffolds as templates design by either rational aided computational modeling, directed evolution, or combination approaches. describing successes designing heme, nonheme Fe, Cu metalloenzymes, heteronuclear containing those other centers (including non-native ions metallocofactors), have summarized insights gained careful controls sphere, including hydrophobic hydrogen bonding interactions, allow generation respective systems approach, rival, and, few cases, exceed We also provided outlook remaining challenges field future directions that will deeper understanding coordintion be gained, turn guide broader more efficient ArMs.

Язык: Английский

Процитировано

114

Machine learning for functional protein design DOI
Pascal Notin, Nathan Rollins, Yarin Gal

и другие.

Nature Biotechnology, Год журнала: 2024, Номер 42(2), С. 216 - 228

Опубликована: Фев. 1, 2024

Язык: Английский

Процитировано

98

Stereoselective amino acid synthesis by synergistic photoredox-pyridoxal radical biocatalysis DOI
Lei Cheng, Dian Li, Binh Khanh

и другие.

Science, Год журнала: 2023, Номер 381(6656), С. 444 - 451

Опубликована: Июль 27, 2023

Developing synthetically useful enzymatic reactions that are not known in biochemistry and organic chemistry is an important challenge biocatalysis. Through the synergistic merger of photoredox catalysis pyridoxal 5'-phosphate (PLP) biocatalysis, we developed a radical biocatalysis approach to prepare valuable noncanonical amino acids, including those bearing stereochemical dyad or triad, without need for protecting groups. Using engineered PLP enzymes, either enantiomeric product could be produced biocatalyst-controlled fashion. Synergistic

Язык: Английский

Процитировано

83

Using enzymes to tame nitrogen-centred radicals for enantioselective hydroamination DOI

Yuxuan Ye,

Jingzhe Cao,

Daniel G. Oblinsky

и другие.

Nature Chemistry, Год журнала: 2022, Номер 15(2), С. 206 - 212

Опубликована: Ноя. 14, 2022

Язык: Английский

Процитировано

78

Engineered enzymes for the synthesis of pharmaceuticals and other high-value products DOI
Manfred T. Reetz, Ge Qu, Zhoutong Sun

и другие.

Nature Synthesis, Год журнала: 2024, Номер 3(1), С. 19 - 32

Опубликована: Янв. 4, 2024

Язык: Английский

Процитировано

74