Photoinduced Borylation for the Synthesis of Organoboron Compounds

Chemical Reviews, Год журнала: 2021, Номер 121(7), С. 3561 - 3597

Опубликована: Фев. 17, 2021

Organoboron compounds have important synthetic value and can be applied in numerous transformations. The development of practical convenient ways to synthesize boronate esters has thus attracted significant interest. Photoinduced borylations originated from stoichiometric reactions alkanes arenes with well-defined metal–boryl complexes. Now, photoredox-initiated borylations, catalyzed by either transition metal or organic photocatalysts, photochemical high efficiency become a burgeoning area research. In this Focus Review, we summarize research on photoinduced especially emphasizing recent developments trends. This includes the borylation arenes, alkanes, aryl/alkyl halides, activated carboxylic acids, amines, alcohols, so based catalysis, metal-free organocatalysis, direct activation. We focus reaction mechanisms involving single-electron transfer, triplet-energy other radical processes.

Язык: Английский

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First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Chemical Reviews, Год журнала: 2021, Номер 121(21), С. 13238 - 13341

Опубликована: Окт. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Язык: Английский

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Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules

Chemical Reviews, Год журнала: 2023, Номер 123(12), С. 7692 - 7760

Опубликована: Май 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Язык: Английский

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Recent advances in asymmetric borylation by transition metal catalysis

Chemical Society Reviews, Год журнала: 2021, Номер 50(23), С. 13129 - 13188

Опубликована: Янв. 1, 2021

We provide a comprehensive overview of transition metal-catalysed asymmetric borylation processes to construct C–B, C–C, and other C–heteroatom bonds with considerable attention devoted the reaction modes mechanisms involved.

Язык: Английский

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Recent advance in the C–F bond functionalization of trifluoromethyl-containing compounds

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(14), С. 3915 - 3942

Опубликована: Янв. 1, 2021

The C–F bond is the strongest single in organic compounds.

Язык: Английский

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Organothianthrenium salts: synthesis and utilization

Chemical Science, Год журнала: 2022, Номер 13(46), С. 13690 - 13707

Опубликована: Янв. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Язык: Английский

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Generation of non-stabilized alkyl radicals from thianthrenium salts for C–B and C–C bond formation

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Июль 26, 2021

Abstract Sulfonium salts bearing a positively charged sulfur atom with three organic substituents have intrigued chemists for more than century their unusual structures and high chemical reactivity. These compounds are known to undergo facile single-electron reduction emerge as valuable alternative source of aryl radicals synthesis. However, the generation non-stabilized alkyl from sulfonium has been challenge several decades. Here we report treatment S -(alkyl) thianthrenium generate key intermediates granting controlled selective outcome ensuing reactions under mild photoredox conditions. The value these reagents demonstrated through efficient construction alkylboronates other transformations, including heteroarylation, alkylation, alkenylation, alkynylation. developed method is practical, provides opportunity convert C–OH bond C–B C–C bonds.

Язык: Английский

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Tetracoordinate Boron Intermediates Enable Unconventional Transformations

Accounts of Chemical Research, Год журнала: 2021, Номер 54(9), С. 2298 - 2312

Опубликована: Апрель 14, 2021

ConspectusOrganoboron compounds are a class of multifunctional reagents for the construction carbon–carbon and carbon–heteroatom bonds in modern synthetic chemistry. The transformations organoboron usually carried out through tetracoordinate boron intermediates mainly include additions to unsaturated bonds, rearrangement reactions, transmetalation so on. Although great progress has been achieved improving intermediates, there still shortcomings, such as sparse activation modes, paucity reaction strategies difficulties stereoselective control. In this Account, we discuss our recent advances development unconventional based on design including following three topics: (1) C–B bonds; (2) C–C (3) application chiral boron.The new build is interest chemists. We have developed tandem reactions involving multiple selective borylations alkynes synthesis stable boron, domino-borylation-protodeboronation (DBP) strategy alkynes, highly regio-, stereo-, chemoselective Cu-catalyzed diborylation β-CF3-1,3-enynes cascade B–Cl/C–B cross-metathesis C–H bond borylation triarylboranes. also novel form because formation an enduring theme organic disclosed long distance or migration coupling partners 1,4-migrations nitrile oxide nitrilium migrations isocyanide intermediate, palladium-catalyzed Suzuki–Miyaura thioureas thioamides, copper-catalyzed atroposelective Michael-type addition, Catellani reaction. Moreover, terms control found that tricoordinate complex could activate water with Brønsted acidity, which successfully applied high enantioselectivity asymmetric catalytic reduction challenging indoles.This Account summarizes efforts using not only precise wide range diverse but acid indoles.

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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Recent advances in visible light-mediated chemical transformations of enaminones

Chinese Chemical Letters, Год журнала: 2023, Номер 35(2), С. 108977 - 108977

Опубликована: Авг. 26, 2023

Язык: Английский

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