Recent Advances in Photoredox-Catalyzed Difunctionalization of Alkenes

Catalysts, Год журнала: 2023, Номер 13(7), С. 1056 - 1056

Опубликована: Июнь 30, 2023

Alkenes and their related analogs are ideal starting materials for organic synthesis, the selective difunctionalization of alkenes, which allows simultaneous introduction two neighboring bonds, has gained considerable attention in recent years. In particular, photoredox-catalyzed alkenes also been accomplished, regarded as an increasingly powerful tool synthesis miscellaneous interesting molecular scaffolds environmentally benign economical manner. Several exquisite strategies have developed to facilitate this transformation, such photosensitizer-catalyzed redox reactions, electron donor-acceptor (EDA) complexes-mediated photoreactions, atom transfer radical addition (ATRA) reactions. This literature review briefly describes most key progress on 1,2-difunctionalization various structurally diverse including 1,2-dicarbofunctionalization, 1,2-carboheterofunctionalization, 1,2-diheterofunctionalization, with a special emphasis mechanistic details.

Язык: Английский

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Organocatalytic radical relay trifunctionalization of unactivated alkenes by a combination of cyano migration and alkylacylation

Chemical Communications, Год журнала: 2023, Номер 59(36), С. 5395 - 5398

Опубликована: Янв. 1, 2023

The first N-heterocyclic carbene organocatalytic three-component radical relay trifunctionalization of unactivated alkenes through the combination remote 1,4-cyano migration and alkylacylation was reported. This protocol features mild reaction conditions, readily available materials, excellent regioselectivity, capability late-stage functionalization.

Язык: Английский

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Nickel-Catalyzed 1,1-Aminoborylation of Unactivated Terminal Alkenes

ACS Catalysis, Год журнала: 2023, Номер 13(8), С. 5538 - 5543

Опубликована: Апрель 10, 2023

Herein, we disclose a Ni-catalyzed 1,1-difunctionalization of unactivated terminal alkenes that enables the incorporation two different heteroatom motifs across an olefin backbone, thus streamlining access to α-aminoboronic acid derivatives from simple precursors. The method is characterized by its simplicity and generality wide number coupling counterparts.

Язык: Английский

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Zinc Catalyzed Hydroelementation (HE; E = B, C, N, and O) of Carbodiimides: Intermediates Isolation and Mechanistic Insights

Organometallics, Год журнала: 2023, Номер 42(14), С. 1746 - 1758

Опубликована: Март 15, 2023

The conjugated bis-guanidinate (CBG) supported zinc hydride, [{LZnH}2; L = {(ArHN)(ArN)-C═N–C═(NAr)(NHAr); Ar 2,6-Et2-C6H3}] (1) (pre)-catalyzed addition of E–H (E B, C, N, and O) to carbodiimides is presented. Compound 1 catalyzed the reduction with pinacolborane (HBpin), terminal alkynes, primary amines, alcohols, gave a series N-boryl formamidines, propiolamidines, guanidines, isoureas high conversions. All these reactions display good tolerance functional groups. These proceeded through active catalysts intermediate amidinate (Zn-1, Zn-1′, Zn-3), alkynyl (Zn-2, Zn-2′), anilide (Zn-4), alkoxide (Zn-5) complexes, which have been characterized by multinuclear NMR HRMS analyses. Moreover, compounds Zn-2′, Zn-4, Zn-5 were confirmed single-crystal X-ray diffraction studies. Complete catalytic cycles proposed based on well-defined intermediates stoichiometric experiments.

Язык: Английский

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Catalyst Complexity in a Highly Active and Selective Wacker-Type Markovnikov Oxidation of Olefins with a Bioinspired Iron Complex

ACS Catalysis, Год журнала: 2023, Номер 13(7), С. 4421 - 4432

Опубликована: Март 17, 2023

Palladium-catalyzed Wacker-type reactions occupy a central place in organic synthesis with important implications industry. Pursuing more benign protocols by replacing palladium first-row transition metals allowed the identification of iron as privileged one last few years. Although anti-Markovnikov selectivity for catalysts is well developed, Markovnikov-selective still afford significant quantities alcohol side-products, and reaction intermediates has remained elusive so far. Herein, we present an catalyst that affords Markovnikov ketone products from (hetero)aromatic aliphatic olefins up to 99% under ambient conditions 190,000 turnover numbers frequencies 74 h–1 at 50 °C. The design based on promiscuous activity encountered family cytochromes P-450 enzymes, it enables formation iron-hydride species catalytically relevant conditions. Substrate scope assessment mechanistic investigations suggest catalytic cycle competes unprecedented three additional cycles (alcohol formation, hydrogenation, reductive homo-coupling) depending nature olefin

Язык: Английский

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Oxidative Three-Component Selenofunctionalization of Alkenes: Convenient Access to Vicinally Functionalized Selenides

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(11), С. 7431 - 7447

Опубликована: Май 23, 2023

Three-component selenofunctionalization processes of olefins, diselenides and sulfonamides, water, alcohols, or acids utilizing 1-fluoropyridinium triflate (FP-OTf) as a reaction promoter are reported. Under the optimal conditions, broad range vicinally functionalized selenide derivatives was accessible with high yields excellent functional group compatibilities. Mechanistic studies revealed that FP-OTf played key role in this process.

Язык: Английский

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Synergistic Brønsted Base/Photoredox‐Catalyzed Three‐Component Coupling with Malonates to Synthesize δ‐Hydroxy Esters and δ‐Keto Esters

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(9), С. 957 - 962

Опубликована: Янв. 18, 2024

Comprehensive Summary Multicomponent alkene 1,2‐dicarbofunctionalizations (DCFs) have emerged as a powerful strategy to rapidly incorporate both two carbon subunits across one C—C double bond in step for enhancing molecular complexity and diversity. To the best of our knowledge, there is only report on photoredox‐catalyzed three‐component DCFs with malonates through radical−radical cross‐coupling, while radical‐polar crossover (RPC)‐type were still rare. Herein, we describe redox‐neutral RPC‐type 1,2‐dialkylation styrenes aldehydes synergistic Brønsted base/photoredox catalysis system. This transition‐metal‐free provides an efficient clean approach broad variety δ‐hydroxy esters also features exceptionally mild conditions, wide compatibility substrate scope functional groups, high atomic economy. Moreover, 1,2‐alkylacylation from same starting materials was achieved one‐pot manner such coupling subsequent two‐electron oxidation process, providing set δ‐keto interest pharmaceutical research.

Язык: Английский

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Photoredox-catalyzed intermolecular azidosulfonylation of alkenes with DABCO·(SO₂)₂, trimethylsilyl azide and thianthrenium salts

Organic Chemistry Frontiers, Год журнала: 2022, Номер 10(4), С. 866 - 871

Опубликована: Дек. 21, 2022

Synthesis of β-azido alkylsulfones through a photoredox-catalyzed azido sulfonylation alkenes with DABCO·(SO 2 ) , trimethylsilyl azide and alkyl thianthrenium salts is developed.

Язык: Английский

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An Oxidative [3+2+1] Cyclization of Enaminones and N‐Alkenyl‐2‐pyrrolidinone: Access to Polysubstituted 4‐Alkylated 1,4‐dihydropyridines

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(8), С. 1217 - 1223

Опубликована: Март 25, 2023

Abstract An oxidative [3+2+1] cyclization of enaminones and N ‐alkenyl‐2‐pyrrolidinone is described for the synthesis 4‐alkylated 1,4‐dihydropyridines (1,4‐DHPs). By using terminal olefin as C4 source 1,4‐DHP skeleton, this synthetic strategy provides a series 1,4‐DHPs through 1,1‐difunctionalization/cyclization process. In protocol, two C( sp 3 )−C( 2 ) bonds )−N bond are simultaneously formed, hydrogen on newly formed methyl group skeleton confirmed possible mechanism proposed. magnified image

Язык: Английский

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EnT‐Mediated Amino‐Sulfonylation of Alkenes with Bifunctional Sulfonamides: Access to β‐Amino Sulfone Derivatives

Chemistry - A European Journal, Год журнала: 2023, Номер 29(43)

Опубликована: Май 23, 2023

Abstract β ‐Amino sulfones are commonly found structural motifs in biologically active compounds. Herein, we report a direct photocatalyzed amino‐sulfonylation reaction of alkenes for the efficicient production important compounds by simple hydrolysis without need additional oxidants and reductants. In this transformation, sulfonamides worked as bifunctional reagents, simultaneously generating sulfonyl radicals N ‐centered which were added to alkene highly atom‐economical fashion with high regioselectivity diastereoselectivity. This approach showed functional group tolerance compatibility, facilitating late‐stage modification some bioactive sulfonamide molecules, thereby expanding relevant chemical space. Scaling up led an efficient green synthesis apremilast, one best‐selling pharmceuticals, demonstrating synthetic utility applied method. Moreover, mechanistic investigations suggest that energy transfer (EnT) process was operation.

Язык: Английский

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