Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Язык: Английский

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Ligand Development for Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Racemic Alkyl Halides

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(38), С. 17319 - 17329

Опубликована: Сен. 1, 2022

The enantioconvergent cross-coupling of racemic alkyl halides represents a powerful tool for the synthesis enantioenriched molecules. In this regard, first-row transition metal catalysis provides suitable mechanism stereoconvergence by converting to prochiral radical intermediates owing their good single-electron transfer ability. contrast noble development chiral nickel catalyst, copper-catalyzed is less studied. Besides enantiocontrol issue, major challenge arises from weak reducing capability copper that slows reaction initiation. Recently, significant efforts have been dedicated basic research aimed at developing ligands halides. This perspective will discuss advances in burgeoning area with particular emphasis on strategic anionic ligand design tune initiation under thermal conditions our group.

Язык: Английский

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Enantioselective [2π + 2σ] Cycloadditions of Bicyclo[1.1.0]butanes with Vinylazaarenes through Asymmetric Photoredox Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 8372 - 8380

Опубликована: Март 18, 2024

Here we present a highly enantioselective [2π + 2σ] photocycloaddition of bicyclo[1.1.0]butanes (BCBs). The reaction uses variety vinylazaarenes as partners and is catalyzed by polycyclic aromatic hydrocarbon (PAH)-containing chiral phosphoric acid bifunctional photosensitizer. A wide array pharmaceutically important bicyclo[2.1.1]hexane (BCH) derivatives have been synthesized with high yields, enantioselectivity, diastereoselectivity. In addition to the diverse 1-ketocarbonyl-3-substituted BCBs, α/β-substituted are compatible such an unprecedented photoredox catalytic pathway, resulting in successful assembly all-carbon quaternary stereocenter or two adjacent tertiary stereocenters on product.

Язык: Английский

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Photocatalysis Meets Confinement: An Emerging Opportunity for Photoinduced Organic Transformations

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Янв. 19, 2024

Abstract The self‐assembled metal‐organic cages (MOCs) have been evolved as a paradigm of enzyme‐mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components constitute microenvironments characteristic enzymatic spatial confinement versatile host–guest interactions, thus facilitating unconventional transformations via unique driving‐forces such weak noncovalent binding electron/energy transfer. Recently, MOC‐based photoreactors emerged burgeoning platform supramolecular photocatalysis, displaying anomalous reactivities selectivities distinct from bulk solution. This perspective recaps two decades journey the photoinduced radical reactions by using photoactive (PMOCs) artificial reactors, outlining how cage‐confined photocatalysis was stoichiometric photoreactions photocatalytic turnover, high‐energy UV‐irradiation sustainable visible‐light photoactivation, simple multi‐level chemo‐ stereoselectivities. We will focus on PMOCs that merge structural functional biomimicry into single‐cage behave multi‐role photoreactors, emphasizing their potentials tackling current challenges through single‐electron transfer (SET) or energy (EnT) pathways simple, green while feasible manner.

Язык: Английский

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Noncanonical Amino Acids in Biocatalysis

Chemical Reviews, Год журнала: 2024, Номер 124(14), С. 8740 - 8786

Опубликована: Июль 3, 2024

In recent years, powerful genetic code reprogramming methods have emerged that allow new functional components to be embedded into proteins as noncanonical amino acid (ncAA) side chains. this review, we will illustrate how the availability of an expanded set building blocks has opened a wealth opportunities in enzymology and biocatalysis research. Genetic provided insights enzyme mechanisms by allowing introduction spectroscopic probes targeted replacement individual atoms or groups. NcAAs also been used develop engineered biocatalysts with improved activity, selectivity, stability, well enzymes artificial regulatory elements are responsive external stimuli. Perhaps most ambitiously, combination laboratory evolution given rise classes use ncAAs key catalytic elements. With framework for developing ncAA-containing now firmly established, optimistic become progressively more tool armory designers engineers coming years.

Язык: Английский

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Recent advances in photo- and electro-enabled radical silylation

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(22), С. 6400 - 6415

Опубликована: Янв. 1, 2022

This review aims to highlight the recent advances in area of radical type silylation reactions mediated by photo- and electrocatalysis.

Язык: Английский

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Enantioselective Radical Addition to Ketones through Lewis Acid-Enabled Photoredox Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(48), С. 22140 - 22149

Опубликована: Ноя. 22, 2022

Photocatalysis opens up a new window for carbonyl chemistry. Despite multitude of photochemical reactions compounds, visible light-induced catalytic asymmetric transformations remain elusive and pose formidable challenge. Accordingly, the development simple, efficient, economic systems is ideal pursuit chemists. Herein, we report an enantioselective radical photoaddition to ketones through Lewis acid-enabled photoredox catalysis wherein in situ formed chiral N,N'-dioxide/Sc(III)-ketone complex serves as temporary photocatalyst trigger single-electron transfer oxidation silanes generation nucleophilic species, including primary, secondary, tertiary alkyl radicals, giving various enantioenriched aza-heterocycle-based alcohols good excellent yields enantioselectivities. The results electron paramagnetic resonance (EPR) high-resolution mass spectrum (HRMS) measurements provided favorable evidence stereocontrolled addition process involved this reaction.

Язык: Английский

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Strategies That Utilize Ion Pairing Interactions to Exert Selectivity Control in the Functionalization of C–H Bonds

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(40), С. 18195 - 18211

Опубликована: Сен. 30, 2022

Electrostatic attraction between two groups of opposite charge, typically known as ion-pairing, offers unique opportunities for the design systems to enable selectivity control in chemical reactions. Catalysis using noncovalent interactions is an established and vibrant research area, but it noticeable that hydrogen bonding are still main interaction choice system design. Opposite charges experience powerful force Coulombic have ability exert fundamental influence on outcome reactions involve charged reagents, intermediates or catalysts. In this Perspective, we will examine how ion-pairing been used C-H bond functionalization processes. This broad class provides interesting thought-provoking lens through which application strategies because one encompasses great mechanistic diversity, poses significant challenges, perhaps most importantly immense interest synthetic chemists both industry academia. We survey proceed via radical ionic mechanisms alongside those transition metal catalysis deal with site-selectivity enantioselectivity. anticipate emerging area develops, become ever-more important strategy control.

Язык: Английский

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The green chemistry paradigm in modern organic synthesis

Russian Chemical Reviews, Год журнала: 2023, Номер 92(12), С. RCR5104 - RCR5104

Опубликована: Дек. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Язык: Английский

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An update on chiral phosphoric acid organocatalyzed stereoselective reactions

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(17), С. 3477 - 3502

Опубликована: Янв. 1, 2023

This review article presents an in-depth analysis of the strategies and methodologies for using chiral phosphoric acids as organocatalysts in asymmetric syntheses from recent literature.

Язык: Английский

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