Electrochemical Difunctionalization of Alkenes

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Abstract Owing to their wide utilizations in synthesis and products prevalence numerous natural products, pharmaceuticals functional materials, the alkene difunctionalization methods for selective transformations of olefins are important have attracted much attention form synthetic chemists. Among them, electrochemical reaction is particularly promising has becoming a potent sustainable tool alkenes into vicinal difunctionalized structures organic through simultaneous incorporation two groups. Herein, we summarize recent progress reactions according types as well category radicals over past five years. By selecting remarkable examples, elaborately discussed substrate scope mechanisms olefin reaction.

Language: Английский

---

Copper-Catalyzed Enantioselective Three-Component Carboamidation of Styrenes with Alkanes and Amides

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

Published: April 4, 2025

Efficient assembly of valuable chiral molecules from readily available and low-cost chemical feedstocks remains one the most challenging tasks in synthetic chemistry today. Radical-mediated three-component carboamination alkenes offers an attractive strategy for addressing this challenge. However, existing reports focus on racemic examples are largely limited to activated alkenes, preactivated alkylation reagents, or sufficiently active nucleophiles. Herein, we report a highly enantioselective carboamidation styrenes with unactivated alkanes weakly nucleophilic amides. Enantioselective control is achieved by using cationic copper catalysts. This method enables synthesis variety optically amides excellent enantioselectivity. Mechanistic studies reveal that reaction proceeds via hydrogen atom transfer alkane followed radical addition olefin.

Language: Английский

---

Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range alkenes, including vinyl arenes, enamides, enol ethers, sulfides, dehydroamino esters, were regioselectively functionalized with an azide nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric oximes, phenols. method led to more efficient synthesis 1,2-azidofunctionalized pharmaceutical intermediates when compared previous approaches, resulting in both reduction step count increase overall yield. scope limitations these transformations further investigated through standard unbiased selection 15 substrate combinations out 1,175,658 possible clustering technique.

Language: Английский

---

Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Abstract The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical‐polar crossover strategy. A broad range alkenes, including vinyl arenes, enamides, enol ethers, sulfides, dehydroamino esters, were regioselectively functionalized with an azide nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric oximes, phenols. method led to more efficient synthesis 1,2‐azidofunctionalized pharmaceutical intermediates when compared previous approaches, resulting in both reduction step count increase overall yield. scope limitations these transformations further investigated through standard unbiased selection 15 substrate combinations out 1,175,658 possible clustering technique.

Language: Английский

---

Iron-Catalyzed Three-Component Reactions of Cyclopropanols with Alkenes and N-Heteroarenes via Ring-Opening and C–H Functionalization

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

Published: May 13, 2025

An iron-catalyzed ring-opening multicomponent reaction of cyclopropyl alcohols with alkenes and N-heteroarenes involving aryl C(sp2)-H functionalization was developed. This protocol facilitates the regioselective introduction both β-carbonyl moiety an N-heteroarene group across C═C bond alkene, thus allowing a straightforward, efficient, facile access to 5-heteroarene ketones. In this process, strategy relies on alkyl radical formation from alcohols, addition bonds, heteroaryl cascades. general approach displays excellent selectivity control broad functional-group tolerance.

Language: Английский

---

Expedient Cyano‐hydroxylation of Alkenes Enabled by Halogen Atom Transfer Induced Radical Ring‐Opening Elaboration of 3‐Bromo‐isoxazoline Cycloadducts

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 19, 2025

Comprehensive Summary Herein, we present a highly efficient one‐pot, two‐step synthesis of β ‐hydroxy nitrile scaffolds, which possess both significant synthetic value and notable biological activity, starting from readily accessible alkenes. This methodology relies crucially on the seamless integration regioselective (3+2) cycloaddition reaction, employing commercially available 1,1‐dibromoformaldoxime as 1,3‐dipole precursor, with subsequent halogen atom transfer‐induced radical ring‐opening elaboration resulting 3‐bromo‐2‐isoxazoline cycloadducts. protocol is featured by mild reaction conditions, broad alkene scope various derivatizations obtained cyano‐hydroxylation products, offering versatile practical pathway to accessing multi‐functionalized molecules.

Language: Английский

---

Reactivity Tuning for Selective Aldimino-Sulfonylation of Styrenes by Photocatalytic Activation of Sulfonyl Aldimines

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

Published: May 31, 2025

Imino-sulfonylation of styrene represents a powerful method for constructing highly functionalized molecules, while only diphenyl imines were able to be employed in previous reports. By modulating the electron property styrene, visible-light-mediated radical/radical cross-coupling aldiminyl radical and carbon-centered was achieved synthesize diverse aldimine-embedded sulfones by using sulfonyl aldimines α-trifluoromethylstyrenes. One-pot oxidation delivered Ritter-type amidation products without need excessive nitriles as solvent. Furthermore, this protocol took advantage simple reaction conditions, good substituent diversity, high atom economy broaden research radicals amination alkenes.

Language: Английский

---

Visible-Light Induced and Iron Peroxo-Promoted Radical Difunctionalization of Alkene for the Synthesis of β-Ketosulfone and α-Chloroketone

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 26, 2024

In this work, a switchable synthesis of β-ketosulfone and α-chloroketone through radical difunctionalization alkenes is reported. The transformation works well under iron peroxo species/photoredox dual catalysis an open-flask atmosphere, the reaction highlighted with good yields broad scope. Mechanism studies show that initiated by formal [4 + 2] cyclization sulfonyl in regioselective manner.

Language: Английский

---