Photocatalysis in the Life Science Industry

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2907 - 2980

Опубликована: Сен. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Язык: Английский

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Ni-electrocatalytic Csp3–Csp3 doubly decarboxylative coupling

Nature, Год журнала: 2022, Номер 606(7913), С. 313 - 318

Опубликована: Апрель 5, 2022

Язык: Английский

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Enantioselective Radical Carbocyanation of 1,3-Dienes via Photocatalytic Generation of Allylcopper Complexes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(11), С. 4168 - 4173

Опубликована: Март 11, 2021

1,3-Dienes are readily available feedstocks that widely used in the laboratory and industry. However, potential of converting 1,3-dienes into value-added products, especially chiral has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve first visible-light-induced, enantioselective carbocyanation by using carboxylic acid derivatives trimethylsilyl cyanide. Under mild neutral conditions, a diverse range allyl cyanides produced generally good efficiency with high enantioselectivity from bench-stable user-safe chemicals. Moreover, preliminary results also confirm this success can be expanded to 1,3-enynes four-component carbonylative 1,3-enynes.

Язык: Английский

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Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(21)

Опубликована: Апрель 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Язык: Английский

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Bridge Functionalisation of Bicyclo[1.1.1]pentane Derivatives

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(47), С. 24754 - 24769

Опубликована: Июнь 21, 2021

"Escaping from flatland", by increasing the saturation level and three-dimensionality of drug-like compounds, can enhance their potency, selectivity pharmacokinetic profile. One approach that has attracted considerable recent attention is bioisosteric replacement aromatic rings, internal alkynes tert-butyl groups with bicyclo[1.1.1]pentane (BCP) units. While functionalisation tertiary bridgehead positions BCP derivatives well-documented, three concyclic secondary bridge remains an emerging field. The unique properties core present synthetic challenges to development such transformations. However, provide novel vectors for drug discovery applications in materials science, providing entry chemical intellectual property space. This Minireview aims consolidate major advances field, serving as a useful reference guide further work expected coming years.

Язык: Английский

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Nickel-Catalyzed Decarboxylative Cross-Coupling of Bicyclo[1.1.1]pentyl Radicals Enabled by Electron Donor–Acceptor Complex Photoactivation

Organic Letters, Год журнала: 2021, Номер 23(12), С. 4828 - 4833

Опубликована: Июнь 8, 2021

The use of bicyclo[1.1.1]pentanes (BCPs) as para-disubstituted aryl bioisosteres has gained considerable momentum in drug development programs. Carbon–carbon bond formation via transition-metal-mediated cross-coupling represents an attractive strategy to generate BCP–aryl compounds for late-stage functionalization, but these typically require reactive organometallics prepare BCP nucleophiles on demand from [1.1.1]propellane. In this study, the synthesis and Ni-catalyzed functionalization redox-active esters with (hetero)aryl bromides action a photoactive electron donor–acceptor complex are reported.

Язык: Английский

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Metal-Free Photosynthesis of Alkylated Benzimidazo[2,1-a]isoquinoline-6(5H)-ones and Indolo[2,1-a]isoquinolin-6(5H)-ones in PEG-200

The Journal of Organic Chemistry, Год журнала: 2021, Номер 86(13), С. 9055 - 9066

Опубликована: Июнь 23, 2021

A visible-light-induced decarboxylation reaction was developed for the synthesis of alkylated benzimidazo[2,1-a]isoquinoline-6(5H)-ones and indolo[2,1-a]isoquinolin-6(5H)-ones under metal-free conditions. Impressively, metal catalysts traditionally volatile organic solvents could be effectively avoided.

Язык: Английский

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Catalytic Decarboxylative Fluorosulfonylation Enabled by Energy-Transfer-Mediated Photocatalysis

Organic Letters, Год журнала: 2022, Номер 24(13), С. 2474 - 2478

Опубликована: Март 9, 2022

Sulfonyl fluorides are useful building blocks in a wide array of fields. Herein, we report catalytic decarboxylative fluorosulfonylation approach for converting abundant aliphatic carboxylic acids to the corresponding sulfonyl fluorides. This transformation is enabled by simple preactivation as aldoxime esters and energy-transfer-mediated photocatalysis. operationally method proceeds with high functional-group tolerance under mild redox-neutral conditions.

Язык: Английский

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Convergent Deboronative and Decarboxylative Phosphonylation Enabled by the Phosphite Radical Trap “BecaP”

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(33), С. 18649 - 18657

Опубликована: Авг. 8, 2023

Carbon-phosphorus bond formation is significant in synthetic chemistry because phosphorus-containing compounds offer numerous indispensable biochemical roles. While there a plethora of methods to access organophosphorus compounds, phosphonylations readily accessible alkyl radicals form aliphatic phosphonates are rare and not commonly used synthesis. Herein, we introduce novel phosphorus radical trap "BecaP" that enables facile efficient phosphonylation under visible light photocatalytic conditions. Importantly, the ambiphilic nature BecaP allows redox neutral reactions with both nucleophilic (activated by single-electron oxidation) electrophilic reduction) precursors. Thus, broad scope feedstock potassium trifluoroborate salts active carboxylate esters could be employed, each class substrate proceeding through distinct mechanistic pathway. The mild conditions applicable late-stage installation phosphonate motifs into medicinal agents natural products, which showcased straightforward conversion baclofen (muscle relaxant) phaclofen (GABAB antagonist).

Язык: Английский

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Photoredox‐Catalyzed Decarboxylative Bromination, Chlorination and Thiocyanation Using Inorganic Salts

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Июль 31, 2023

Abstract Decarboxylative halogenation reactions of alkyl carboxylic acids are highly valuable for the synthesis structurally diverse halides. However, many reported protocols rely on stoichiometric strong oxidants or electrophilic halogenating agents. Herein, we describe visible‐light photoredox‐catalyzed decarboxylative N ‐hydroxyphthalimide‐activated that avoid and use inexpensive inorganic halide salts as Bromination with lithium bromide proceeds under simple, transition‐metal‐free conditions using an organic photoredox catalyst no other additives, whereas dual photoredox‐copper catalysis is required chlorination chloride. The mild display excellent functional‐group tolerance, which demonstrated through transformation a range complex acid containing natural products into corresponding bromides chlorides. In addition, show generality photoredox‐copper‐catalyzed functionalization by extension to thiocyanation potassium thiocyanide, was applied thiocyanates.

Язык: Английский

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