Catalytic asymmetric photocycloaddition reactions mediated by enantioselective radical approaches

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The use of olefins in the construction cyclic compounds represents a powerful strategy for advancing pharmaceutical industry.

Language: Английский

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Asymmetric Photoredox Catalytic Minisci-Type Reactions of α-Bromide Amides

Organic Letters, Journal Year: 2025, Volume and Issue: 27(5), P. 1244 - 1249

Published: Jan. 23, 2025

An asymmetric photoredox catalytic Minisci-type reaction between α-bromide amides and imine-containing azaarenes has been successfully developed. This catalyst system employs a chiral phosphoric acid alongside 3DPAFIPN as photosensitizer. The produces diverse array of valuable amides, featuring azaarene-substituted tertiary carbon stereocenters at the β-position, in high yields (up to 85%) good excellent enantioselectivities >99% enantiomeric excess (ee)). Importantly, this work marks first example radical addition simple utilizing radicals functionalized with electron-withdrawing carbonyl groups, which are conventionally considered unfavorable for such transformations, especially an enantioselective manner.

Language: Английский

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Chiral Primary Amine-Catalyzed Asymmetric Photochemical Reactions of Pyridotriazoles with Boronic Acids to Access Triarylmethanes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Imine-containing azaarene-based triarylmethanes are vital molecular motifs that prevalent in a wide array of bioactive compounds. Recognizing the limitations current synthetic methodologies─marked by scarcity examples and difficulties flexible functional group modulation─we have developed an efficient modular asymmetric photochemical strategy employing pyridotriazoles boronic acids as substrates. Utilizing novel chiral diamine-derived pyrroles primary amines catalysts, we successfully synthesized diverse range with high yields excellent enantioselectivities. This method not only exhibits broad substrate scope outstanding tolerance but also enables precise synthesis deuterated derivatives using inexpensive D2O deuterium source. Mechanistic studies reveal unusual 1,4-boron shift is critical step generating boronated enamine intermediate, while shedding light on potential enantiocontrol mechanisms facilitated catalyst.

Language: Английский

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Construction of Anthracene‐based Metal–Organic Framework Exhibiting Enhanced Singlet Oxygen Storage and Release Capabilities for Efficient Photodegradation of Phenolic Pollutants

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 29, 2024

Abstract Controlling the generation and release of singlet oxygen ( 1 O 2 ) with high oxidation activity long lifetime properties holds significant potential for efficient permanent organic pollutants, tumor eradication, targeted molecular oxidation. However, conditions controlled remain unclear. Hence, novel anthracene‐ligands based Zr‐MOFs which use acetic acid (HAc) are constructed to optimize surface defects specific area exhibit ultrafast saturation adsorption capacity (362.60 mg g −1 in 60 s) deep photodegradation performance toward bisphenol A (BPA) water (50 ppm 20 min) via Zr‐DPA MOF‐1HAc. Mechanistic studies have shown that MOFs capable generating concentrations , while anthracene ligands can rapidly store form endoperoxides (EPOs), be released under external light, heat, or chemical triggering conditions. Thus, concentration is always involved reaction throughout whole process ultimately achieves complete mineralization target phenolic pollutant molecules. This innovative strategy has important implications generating, storing controlling field environmental engineering synthesis.

Language: Английский

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Divergent photoreduction of nitroaromatic compounds catalysed by dithienoquinoxaline

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 116033 - 116033

Published: Feb. 1, 2025

Language: Английский

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Palladium-Catalyzed Dearomative para-/ortho-Cycloaddition Cascades of N-Allylanilines with 1,4-Enynes and CO via Skeletal Reorganization

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

A selectivity-control approach for palladium-catalyzed dearomative para-/ortho-cycloaddition cascades of aromatic compounds with 1,4-enynes and CO via a skeletal reorganization process to produce polycycle-fused bicyclo[2.2.2]octenes is reported. This mechanistically novel depends on that consists sequence [4 + 2] para-cycloaddition, 3,3-Cope rearrangement, carbon–carbon bond activation/[4 cycloaddition.

Language: Английский

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Construction of Chiral Spiro-Bridged Rings with Four Consecutive Stereocenters via Dearomative Diels–Alder Reactions of Anthracenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

A highly diastereo- and enantioselective dearomative Diels-Alder reaction was accomplished by chiral N,N'-dioxide/Mg(II) complex catalyst. Various anthracene derivatives methyleneindolinones efficiently transformed into the corresponding spiro-bridged cyclic products with four consecutive stereocenters in good yields, excellent dr er values under mild conditions (46 examples, up to 99% yield, >19:1 dr, >99:1 er). Gram-scale synthesis of their further transformations were feasible. On basis theoretical calculation, possible working modes provided understand origin stereoselectivity this transformation.

Language: Английский

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Sequential C–H Aroylation and Formal [4 + 2] Cycloaddition of Naphthalenes with Aroylfluorides and Styrenes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 10406 - 10415

Published: June 4, 2025

Language: Английский

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Photocatalytic intermolecular dearomative cycloaddition of phenanthrenes and naphthalenes with excited gem-difluoroalkenes

Chem Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 101200 - 101200

Published: Dec. 1, 2024

Language: Английский

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