C(sp³)−H (N‐Phenyltetrazole)thiolation as an Enabling Tool for Molecular Diversification

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 24, 2024

Abstract Methods enabling the broad diversification of C(sp 3 )−H bonds from a common intermediate are especially valuable in chemical synthesis. Herein, we report site‐selective ( N ‐phenyltetrazole)thiolation aliphatic and (hetero)benzylic using commercially available disulfide to access ‐phenyltetrazole thioethers. The thioether products readily elaborated diverse fragment couplings for C−C, C−O, or C−N construction. C−H functionalization proceeds via radical‐chain pathway involving hydrogen atom transfer by electron‐poor ‐phenyltetrazolethiyl radical. Hexafluoroisopropanol was found be essential reactions thiolation, with computational analysis consistent dual bonding radical imparting increased electrophilicity facilitate transfer. Substrate is limiting reagent all cases, reaction displays an exceptional functional group tolerance well suited applications late‐stage diversification.

Language: Английский

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γ-Amino C(sp³)–H Functionalization of Aliphatic Amines through a Light-Driven Triple Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 8005 - 8012

Published: May 9, 2024

We report intra- and intermolecular γ-amino C(sp3)–H functionalization of aliphatic amines using a vinylsulfone-based HAT (hydrogen atom transfer) auxiliary triple catalysis, which is composed photoredox, cobalt, Brønsted acid catalysts under visible light irradiation. The process accomplishes four elementary steps: (i) electrophilic carbon-centered radical formation on the via MHAT (metal hydride hydrogen reaction, (ii) generation through 1,6-HAT (iii) single-electron oxidation to carbocation equivalents, (iv) nucleophilic substitution with internal or external nucleophiles. As result, this afforded γ-amino-functionalized products, such as azetidines, 1,3-diamine, 1,3-aminoalcohol derivatives.

Language: Английский

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Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21257 - 21263

Published: July 26, 2024

Because of their robustness and orthogonal reactivity features, alkyl germanes bear significant potential as functional handles for the construction C(sp3)-rich scaffolds, especially in context modular synthetic approaches. However, to date, only radical-based has been accessible from these handles, which limits types possible decorations. Here, we describe first general C(sp3)–heteroatom bond formation (−GeEt3) by leveraging electrochemistry unlock polar reactivity. This approach allowed us couple C(sp3)–GeEt3 with a variety nucleophiles construct ethers, esters, amines, amides, sulfonamides, sulfides, well C–P, C–F, C–C bonds. The compatibility electrochemical strategy C1 motif was also showcased, involving sequential functionalization Cl, Bpin, ultimately GeEt3 via electrochemistry.

Language: Английский

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Copper‐Catalyzed Fluoroamide‐Directed Remote C(sp³)‐H Bond Functionalization Through Intramolecular Hydrogen Atom Transfer

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(13)

Published: Feb. 15, 2024

Abstract Direct C−H functionalization is an important strategy for the rapid synthesis of valuable organic molecules. Radical‐involved remote C(sp 3 )‐H based on hydrogen atom transfer (HAT) becomes method enabling selective direct transformation bonds at specific distal position(s). In recent years, copper‐catalyzed fluoroamide‐directed bond through intramolecular HAT has served as a robust and elegant assembly variety functionalized (sulfon)amides related derivatives. This review focuses advances in this area. These transformations proceed effectively with high selectivities good functional group compatibility under mild conditions.

Language: Английский

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Photocatalytic acceptorless dehydrogenation of flavanones by cationic Eosin Y as a bifunctional catalyst

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We report the first example of photocatalytic acceptorless dehydrogenation using cationic Eosin Y as a bifunctional photocatalyst, without metal catalysts or HAT reagents.

Language: Английский

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Alkylazolation of Alkenes via Photocatalytic Radical Polar Crossover

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

Published: Jan. 13, 2025

We present a photocatalytic method for alkylamination of alkenes, enabling efficient C-C and C-N bond formation to construct aza-heterocycles valuable in drug discovery. Using radical-polar crossover pathway, electron-deficient alkenes are reduced electrophilic radicals, which react with electron-rich form nucleophilic radicals. Oxidation these intermediates yields carbocations, trapped by aza-heteroarenes afford alkylaminated products. This strategy enhances molecular complexity while suppressing side reactions.

Language: Английский

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Visible-Light-Induced Secondary Benzylic C(sp³)–H Functionalization for Nucleophilic Substitution: An Intermolecular C–X (C–N, C–C, and C–Br) Bond Forming Reaction

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Exploring new synthetic methods that harness visible light represents a breakthrough in organic synthesis. Amides, amines, nitriles, and halides are essential functional groups serve as key building blocks the synthesis of complex molecules medicinal chemistry. This study introduces novel intermolecular benzylic C–X (C–N, C–C, C–Br) bond formation via photoredox C(sp3)–H bonds. methodology enables secondary amides, through reacting substrates with readily accessible reagents including BocNH2, benzamide, acetamide, TMSCN, TBAB. approach displays potential being sustainable efficient to afford amidation, cyanation, halogenation products good yields.

Language: Английский

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Visible-Light-Responsive Tetranuclear Ir-Based Polyoxometalates Achieve Photocatalytic Baeyer–Villiger Oxidation of Ketones

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Synthesizing efficient photocatalysts with a broad-spectrum response is crucial for improving solar energy utilization. In this work, we have constructed two examples of tetrameric Ir-based polyoxometalates by introducing an Ir ion. The introduction ions lowers the band gap energy, and light absorption range extended into visible region. Both displayed satisfactory reactivity visible-light-catalyzed Baeyer-Villiger reaction cyclohexanone, especially compound 1, which reacted up to 95.1% yield 3 h TON TOF values 951 510 h-1, respectively. Meanwhile, 1 also presents excellent cyclic structural stability, can still reach 92.2% after five reactions.

Language: Английский

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Diversification of acridinium photocatalysts: Property tuning and reactivity in model reactions

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: 160, P. 155546 - 155546

Published: March 23, 2025

Language: Английский

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Ni-Doped Perovskite for Photocatalytic Benzylic C–H Amination

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

Published: May 8, 2025

Directly introducing aliphatic or aromatic amines into C(sp3)-H bonds remains a significant challenge in organic synthesis. One major difficulty is that activation an oxidative process, whereas are generally more prone to oxidation than C-H bonds, making them difficult use directly. Typically, protected employed and then deprotected realize amination, but this strategy limits the synthesis of tertiary amines, as secondary often inactive such reactions. Here, we present mild photocatalytic method overcomes these limitations by utilizing Ni-doped perovskite CsPbBr3 nanocrystals (NCs) for benzylic amination directly using unprotected amines. Perovskite enables highly selective activation, while doped Ni(II) readily captures radicals via addition. XPS studies successfully validate addition step with Ni(II)/Ni(III) configuration. Our methodology forges aliphatic, cyclic acyclic, provides powerful tool late-stage functionalization bioactive compounds drug derivatives.

Language: Английский

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