Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2752 - 2906

Published: Aug. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Language: Английский

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Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

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Porous organic polymers for light-driven organic transformations

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2444 - 2490

Published: Jan. 1, 2022

As a new generation of porous materials, organic polymers (POPs), have recently emerged as powerful platform heterogeneous photocatalysis. POPs are constructed using extensive synthesis methodologies, with various functional units being connected via high-energy covalent bonds. This review systematically presents the recent advances in for visible-light driven transformations. Herein, we firstly summarize common construction strategies POP-based photocatalysts based on two major approaches: pre-design and post-modification; secondly, categorize methods reaction types constructing POPs. We then classify introduce specific reactions current light-driven POP-mediated Finally, outline state development problems faced transformations by POPs, present some perspectives to motivate reader explore solutions these confront challenges process.

Language: Английский

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Nickel/Photo-Cocatalyzed Asymmetric Acyl-Carbamoylation of Alkenes

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(5), P. 2180 - 2186

Published: Jan. 23, 2020

An unprecedented asymmetric acyl-carbamoylation of pendant alkenes tethered on aryl carbamic chlorides with both aliphatic and aromatic aldehydes has been developed via the cooperative catalysis a chiral nickel-PHOX complex tetrabutylammonium decatungstate. This reaction represents first example merging hydrogen-atom-transfer photochemistry transition metal in difunctionalization alkenes. Using this protocol, variety oxindoles bearing challenging quaternary stereogenic center are furnished under mild conditions highly enantioselective manner.

Language: Английский

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Exploiting attractive non-covalent interactions for the enantioselective catalysis of reactions involving radical intermediates

Nature Chemistry, Journal Year: 2020, Volume and Issue: 12(11), P. 990 - 1004

Published: Oct. 19, 2020

Language: Английский

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Applications of Nanomaterials in Asymmetric Photocatalysis: Recent Progress, Challenges, and Opportunities

Advanced Materials, Journal Year: 2020, Volume and Issue: 33(6)

Published: July 16, 2020

Abstract Asymmetric catalysis is one of the most attractive strategies to obtain important enantiomerically pure chemicals with high quality and production. In addition, thanks abundant sustainable advantages solar energy, photocatalysis possesses great potential in environmentally benign reactions. Undoubtedly, asymmetric meets strict demand modern chemistry: friendly energy‐sustainable alternatives. Compared homogeneous photocatalysis, heterogeneous has features easy separation, recovery, reuse merits, thus being cost‐ time‐effective. Herein, state‐of‐the‐art progress by nanomaterials addressed. The discussion comprises two sections based on type nanomaterials: typical inorganic semiconductors like TiO 2 quantum dots emerging porous materials including metal–organic frameworks, organic polymers, cages. Finally, challenges future developments are proposed.

Language: Английский

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A review of enantioselective dual transition metal/photoredox catalysis

Science China Chemistry, Journal Year: 2020, Volume and Issue: 63(5), P. 637 - 647

Published: April 1, 2020

Language: Английский

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Photoinduced copper-catalyzed enantioselective coupling reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(7), P. 2358 - 2376

Published: Jan. 1, 2023

This review highlights the progress in photoinduced copper-catalyzed enantioselective coupling reactions.

Language: 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, Journal Year: 2024, Volume and Issue: 146(12), P. 8372 - 8380

Published: March 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.

Language: Английский

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Catalytic Reductive Cross Coupling and Enantioselective Protonation of Olefins to Construct Remote Stereocenters for Azaarenes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(10), P. 4024 - 4031

Published: March 2, 2021

A novel enantioselective protonation protocol that is triggered by reductive cross coupling of olefins reported. When under cooperative photoredox and chiral hydrogen-bonding catalytic conditions using a terminal reductant, various α-branched vinylketones with diverse vinylazaarenes could provide important enantioenriched azaarene derivatives containing tertiary stereocenters at their remote δ-position high yields enantioselectivities. This reaction system also suitable for vinylazaarenes, thus successfully assembling elusive 1,4-stereocenters. The convenient late-stage modifications products, especially the formation ε-tertiary ε-heteroquaternary carbon stereocenters, further highlight synthetic value this method. Control experiments density functional theory (DFT) calculations were conducted to elucidate plausible mechanism origins regioselectivity stereoselectivity.

Language: Английский

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