Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization of Alkenes

Journal of the American Chemical Society, Год журнала: 2018, Номер 141(2), С. 1074 - 1083

Опубликована: Дек. 18, 2018

An asymmetric intermolecular, three-component radical-initiated dicarbofunctionalization of 1,1-diarylalkenes with diverse carbon-centered radical precursors and electron-rich heteroaromatics by a copper(I) chiral phosphoric acid cooperative catalysis strategy has been developed, providing straightforward access to triarylmethanes bearing quaternary all-carbon stereocenters high efficiency as well excellent chemo- enantioselectivity. The key success is not only the introduction sterically demanding favor difunctionalization over otherwise remarkable side reactions but also in situ generation carbocation intermediates from benzylic realize induction aid removable hydroxy directing group via interactions phosphate. Density functional theory calculations elucidated critical environment created hydrogen-bonding ion-pair between catalyst substrates, which leads enantioselective C-C bond formation.

Язык: Английский

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Dual Photoredox/Nickel‐Catalyzed Three‐Component Carbofunctionalization of Alkenes

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(35), С. 12286 - 12290

Опубликована: Июнь 26, 2019

Abstract The potential of merging photoredox and nickel catalysis to perform multicomponent alkene difunctionalizations under visible‐light irradiation is demonstrated here. Secondary tertiary alkyl groups, as well sulfonyl moieties can be added the terminal position double bond with simultaneous arylation internal carbon atom in a single step mild reaction conditions. process, devoid stoichiometric additives, benefits from use bench‐stable easy‐to‐handle reagents, operationally simple, tolerates wide variety functional groups.

Язык: Английский

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Deoxygenative Borylation of Secondary and Tertiary Alcohols

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(28), С. 9561 - 9564

Опубликована: Май 3, 2019

Abstract Two different approaches for the deoxygenative radical borylation of secondary and tertiary alcohols are presented. These transformations either proceed through a metal‐free silyl‐radical‐mediated pathway or utilize visible‐light photoredox catalysis. Readily available xanthates methyl oxalates used as precursors. The reactions show broad substrate scope high functional‐group tolerance, conducted under mild practical conditions.

Язык: Английский

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Visible Light-Induced Borylation of C–O, C–N, and C–X Bonds

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(3), С. 1603 - 1613

Опубликована: Янв. 3, 2020

Boronic acids are centrally important functional motifs and synthetic precursors. Visible light-induced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic method that can effect of wide range substrates, including strong C–O bonds, remains elusive. Herein, we report general, metal-free visible platform enables electron-rich derivatives phenols anilines, chloroarenes, as well other haloarenes. The reaction exhibits excellent group tolerance, demonstrated by the complex substrates. Remarkably, is catalyzed phenothiazine, simple organic photocatalyst with MW < 200 mediates previously unachievable single electron reduction phenol potentials negative approximately – 3 V versus SCE proton-coupled transfer mechanism. Mechanistic studies point crucial role photocatalyst–base interaction.

Язык: Английский

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Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

Beilstein Journal of Organic Chemistry, Год журнала: 2021, Номер 17, С. 771 - 799

Опубликована: Апрель 6, 2021

The reversible, weak ground-state aggregate formed by dipole–dipole interactions between an electron donor and acceptor is referred to as electron-donor–acceptor (EDA) complex. Generally, upon light irradiation, the EDA complex turns into excited state, causing transfer give radicals initiate subsequent reactions. Besides external energy source, reactions involving participation of complexes are mild, obviating transition metal catalysts or photosensitizers in majority cases line with theme green chemistry. This review discusses synthetic concerned well mechanisms that have been shown over past five years.

Язык: Английский

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Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

Asian Journal of Organic Chemistry, Год журнала: 2021, Номер 10(4), С. 711 - 748

Опубликована: Фев. 11, 2021

Abstract Photocatalyzed organic synthesis transformation is a remarkable green synthetic strategy because of the advantages operational simplicity, high chemoselectivities, cheap, and environmental benignancy, along with extensive applications in fields organic, pharmaceutical functional material chemistry. Generally, photoredox catalysts or photosensitizers are necessary for generation their excited states to perform successive oxidative reductive reactions through single electron transfer (SET) energy (ET) process. Furthermore, exploration colored donor‐acceptor (EDA) complex charge (CT) between an electron‐rich electron‐poor substrate provides chance deliver intermediate under irradiation light, resulting formation radical activate species induce various reactions. These were performed without need any external photocatalysts mild reaction conditions. Herein, this review focuses on recent progress photoinduced addition reactions, borylations, radical‐radical cross‐coupling degradation cascade cyclization via EDA complexes. We highlight these novel methodologies applications, as well mechanisms. This will help provide references medicinal chemists who charmed by photochemical transformations based

Язык: Английский

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Exploiting the sp2 character of bicyclo[1.1.1]pentyl radicals in the transition-metal-free multi-component difunctionalization of [1.1.1]propellane

Nature Chemistry, Год журнала: 2022, Номер 14(9), С. 1068 - 1077

Опубликована: Июль 21, 2022

Язык: Английский

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Decarboxylative Borylation and Cross-Coupling of (Hetero)aryl Acids Enabled by Copper Charge Transfer Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(14), С. 6163 - 6172

Опубликована: Апрель 4, 2022

We report a copper-catalyzed strategy for arylboronic ester synthesis that exploits photoinduced ligand-to-metal charge transfer (LMCT) to convert (hetero)aryl acids into aryl radicals amenable ambient-temperature borylation. This near-UV process occurs under mild conditions, requires no prefunctionalization of the native acid, and operates broadly across diverse aryl, heteroaryl, pharmaceutical substrates. also one-pot procedure decarboxylative cross-coupling merges catalytic LMCT borylation palladium-catalyzed Suzuki-Miyaura arylation, vinylation, or alkylation with organobromides access range value-added products. The utility these protocols is highlighted through development heteroselective double-decarboxylative C(sp2)-C(sp2) coupling sequence, pairing halogenation processes two distinct (including substrates) subsequent cross-coupling.

Язык: Английский

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Terminal C(sp ³ )–H borylation through intermolecular radical sampling

Science, Год журнала: 2024, Номер 383(6682), С. 537 - 544

Опубликована: Фев. 1, 2024

Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp

Язык: Английский

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Light‐Driven Synthesis and Functionalization of Bicycloalkanes, Cubanes and Related Bioisosteres

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Янв. 5, 2024

Bicycloalkanes, cubanes and their structural analogues have emerged as bioisosteres of (hetero)arenes. To meet increasing demand, the chemical community has developed a plethora novel synthetic methods. In this review, we assess progress made in field light-driven construction functionalization such relevant molecules. We focused on diverse targets, well reaction processes giving access to: (i) [1.1.1]-bicyclopentanes (BCPs); (ii) [2.2.1]-bicyclohexanes (BCHs); (iii) [3.1.1]-bicycloheptanes (BCHeps); (iv) cubanes; other structurally related scaffolds. Finally, future perspectives dealing with identification manifolds to new functionalized bioisosteric units are discussed.

Язык: Английский

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