Catalyst-Free Selective Synthesis of E-Tetrasubstituted Olefins via Tandem Reaction of 3-Acetyl-4-phenyl-1-oxaspiro[4.5]deca-3,6,9-triene-2,8-dione with Amine, C–C Bond Breakage, and Proton Transfer

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

The Z- or E-selective syntheses of tetrasubstituted olefins present big challenges. Tremendous efforts are ongoing to overcome this issue, especially for acyclic structures. In work, an E-stereoselective synthetic method through tandem reaction 1,4-Michael addition 3-acetyl-4-phenyl-1-oxaspiro[4.5]deca-3,6,9-triene-2,8-dione with amine, C-C bond breakage, and proton transfer by intermolecular hydrogen bonds was revealed excellent atom economy without catalysts additives. A diverse set E-tetrasubstituted were obtained in 43% 93% yields functional group tolerance late-stage modifications complex drug molecules. mechanism proposed based on the deuterium-labeling experiment density theory (DFT) calculation.

Язык: Английский

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Sulfonamide-directed site-selective functionalization of unactivated C(sp3)−H enabled by photocatalytic sequential electron/proton transfer

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 14, 2024

Abstract The generation of alkyl radical from C(sp 3 )−H substrates via hydrogen atom abstraction represents a desirable yet underexplored strategy in alkylation reaction since involving common concerns remain adequately unaddressed, such as the harsh conditions, limited substrate scope, and employment noble metal- or photo-catalysts stoichiometric oxidants. Here, we utilize synergistic photoredox transfer (HAT) catalysis to accomplish general practical functionalization unactived centers with broad high functional group compatibility, operational simplicity. A combination validation experiments density theory reveals that N-centered radicals, generated free N − H bond stepwise electron/proton event, are key intermediates enable an intramolecular 1,5-HAT intermolecular HAT process for nucleophilic carbon-centered radicals formation achieve heteroarylation, alkylation, amination, cyanation, azidation, trifluoromethylthiolation, halogenation deuteration. value this protocol is further demonstrated by gram-scale synthesis late-stage natural products drug derivatives.

Язык: Английский

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Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Green Chemistry, Год журнала: 2024, Номер 26(4), С. 1846 - 1875

Опубликована: Янв. 1, 2024

Organocatalytic enantioselective cross-dehydrogenative coupling reaction provides a great opportunity for the synthesis of highly enantioenriched molecules. In this review, recent progress in field is summarized.

Язык: Английский

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Cooperative Phosphine-Photoredox Catalysis Enables N–H Activation of Azoles for Intermolecular Olefin Hydroamination

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 20349 - 20356

Опубликована: Июль 10, 2024

Catalytic intermolecular olefin hydroamination is an enabling synthetic strategy that offers direct and atom-economical access to a variety of nitrogen-containing compounds from abundant feedstocks. However, despite numerous advances in catalyst design reaction development, N-H azoles with unactivated olefins remains unsolved problem synthesis. We report dual phosphine photoredox catalytic protocol for the structurally diverse medicinally relevant olefins. Hydroamination proceeds high anti-Markovnikov regioselectivity

Язык: Английский

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Recent Advance in Electrochemical C(sp²)—H Amination of Arenes

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(3), С. 871 - 871

Опубликована: Янв. 1, 2024

Язык: Английский

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HAT‐Promoted Electrochemical Amination: C(sp²)−H/N−H Cross Dehydrogenative Coupling

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(5), С. 747 - 752

Опубликована: Фев. 9, 2023

Abstract A direct amination of quinoxalin‐2(1 H )‐ones via electrochemical C( sp 2 )−H/N−H cross dehydrogenative coupling was established by using TMSN 3 as the hydrogen atom transfer (HAT) reagent. Remarkable features this synthetic strategy include operational simplicity, transition metal‐ and chemical oxidant‐free conditions, broad functional group tolerance. wide range primary, secondary amines quinoxalinones are tolerated, giving corresponding tertiary products in good to excellent yields. magnified image

Язык: Английский

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The literature of heterocyclic chemistry, part XXII, 2022

Advances in heterocyclic chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

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C−P Bond Formation by Nickel or Cobalt Catalyzed Coupling Reactions

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract This review discloses nickel‐ and cobalt‐catalyzed coupling reactions that allow C−P bond formation. Activation of C−halide bonds to form phosphonium, pentavalent phosphorus, or trivalent phosphorous compounds has been reported with both metals. However, the conversion C−O ((activated) ethers, carbonates, acetates) into ones only described Ni. Similarly, there are more examples C−Y (Y=C, S, N, B) activations catalyzed by Ni than Co. Nevertheless, cross‐dehydrogenative reaction between a P−H reagent C−H often cobalt nickel. In addition, for metals, electrolytic photocatalytic processes have shown produce variety containing molecules. aims provide an overview potential metals formation highlight remaining challenges.

Язык: Английский

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Photocatalytic Oxidative C(sp³)-H/N–H Cross-Dehydrogenative Coupling of Tertiary Anilines with Amides/Imides: Synthesis of N-Mannich Bases

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 30, 2025

A photocatalytic method for the synthesis of N-Mannich bases has been developed through C(sp3)-H/N-H cross-dehydrogenative coupling N,N-dimethylanilines with amides/imides. This process utilizes 2,4,6-triphenylpyrylium tetrafluoroborate (TPT) as photocatalyst and is conducted at ambient temperature atmospheric air. Various aromatic, heteroaromatic aliphatic (cyclic) amides, well imides were successfully employed, yielding moderate to good results. Preliminary mechanistic isotope-labeling studies indicate that reaction likely proceeds via a single electron transfer pathway involves an α-aminoalkyl radical intermediate.

Язык: Английский

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Anodic Dehydrogenative Aromatization of Tetrahydrocarbazoles Leading to Carbazoles

Organic Letters, Год журнала: 2023, Номер 25(28), С. 5339 - 5344

Опубликована: Июль 10, 2023

Anodic oxidation-promoted aromatization of 1,2,3,4-tetrahydrocarbazoles was achieved. Nitrogen-protected tetrahydrocarbazoles could be converted to the corresponding carbazoles with use bromide as a mediator. LiBr, an inexpensive source, allowed for efficient transformation in presence AcOH.

Язык: Английский

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