Photocatalytic C(sp³) radical generationviaC–H, C–C, and C–X bond cleavage

Chemical Science, Год журнала: 2022, Номер 13(19), С. 5465 - 5504

Опубликована: Янв. 1, 2022

C(sp 3 ) radicals (R˙) are of broad research interest and synthetic utility.

Язык: Английский

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New avenues for C–B bond formationviaradical intermediates

Chemical Science, Год журнала: 2019, Номер 10(37), С. 8503 - 8518

Опубликована: Янв. 1, 2019

Efficient radical routes to important alkyl and aryl boronic esters have been developed over the past few years. Such reactions are complementary existing transition-metal catalysed cross coupling processes.

Язык: Английский

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Dynamic Kinetic Cross-Electrophile Arylation of Benzyl Alcohols by Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2020, Номер 143(1), С. 513 - 523

Опубликована: Дек. 28, 2020

Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report dynamic kinetic approach for the direct functionalization alcohols. The feasibility this strategy demonstrated by nickel-catalyzed cross-electrophile arylation reaction benzyl with (hetero)aryl electrophiles. proceeds broad substrate scope both coupling partners. electron-rich, electron-poor, and ortho-/meta-/para-substituted electrophiles (e.g., Ar–OTf, Ar–I, Ar–Br, inert Ar–Cl) all coupled well. Most functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar–SiMe3, Ar–Bpin, Ar–SnBu3, were tolerated. nature method enables benzylic alcohol in presence various nucleophilic groups, nonactivated primary/secondary/tertiary alcohols, phenols, free indoles. It thus offers robust alternative to existing methods precise construction diarylmethanes. synthetic utility was concise synthesis biologically active molecules its application peptide modification conjugation. Preliminary mechanistic studies revealed that situ formed oxalates nickel, possibly radical process, an initial step aryl

Язык: Английский

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Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(11), С. 4370 - 4374

Опубликована: Янв. 7, 2020

A modular, site-selective 1,2-dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and characterized by excellent chemo- regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple accessible precursors.

Язык: Английский

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Photoinduced Deoxygenative Borylations of Aliphatic Alcohols

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(52), С. 18830 - 18834

Опубликована: Окт. 15, 2019

A photochemical method for converting aliphatic alcohols into boronic esters is described. Preactivation of the alcohol as a 2-iodophenyl-thionocarbonate enables novel Barton-McCombie-type radical deoxygenation that proceeds efficiently with visible light irradiation and without requirement photocatalyst, initiator, or tin silicon hydrides. The resultant alkyl intercepted by bis(catecholato)diboron, furnishing from diverse range structurally complex alcohols.

Язык: Английский

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Radical Dehydroxylative Alkylation of Tertiary Alcohols by Ti Catalysis

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(39), С. 16787 - 16794

Опубликована: Сен. 4, 2020

Deoxygenative radical C–C bond-forming reactions of alcohols are a long-standing challenge in synthetic chemistry, and the current methods rely on multistep procedures. Herein, we report direct dehydroxylative alkylation reaction tertiary alcohols. This new protocol shows feasibility generating carbon radicals from offers an approach for facile precise construction all-carbon quaternary centers. The proceeds with broad substrate scope activated alkenes. It can tolerate wide range electrophilic coupling partners, including allylic carboxylates, aryl vinyl electrophiles, primary alkyl chlorides/bromides, making method complementary to cross-coupling is highly selective alcohols, leaving secondary/primary (benzyl included) phenols intact. utility highlighted by its 10-g-scale late-stage modification complex molecules. A combination experiments density functional theory calculations establishes plausible mechanism implicating generated via Ti-catalyzed homolysis C–OH bond.

Язык: Английский

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Silaboration of [1.1.1]Propellane: A Storable Feedstock for Bicyclo[1.1.1]pentane Derivatives

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(5), С. 1970 - 1974

Опубликована: Окт. 11, 2019

The silaboration of [1.1.1]propellane enables direct introduction B and Si functional groups onto the bicyclo[1.1.1]pentane (BCP) scaffold in high yield under mild, additive-free conditions. silaborated BCP can be obtained on a gram-scale single step without need for column-chromatographic purification, is storable easy to handle, providing versatile synthetic intermediate derivatives. We also describe various conversions C-B/C-Si bonds scaffold, including development modified Suzuki-Miyaura cross-coupling reaction at highly sterically hindered bridgehead sp3 carbon center skeleton using combination activated boronic esters, copper(I) oxide, PdCl2 (dppf) catalyst system.

Язык: Английский

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Dual Catalytic Strategy for Forging sp²–sp³and sp³–sp³Architectures via β-Scission of Aliphatic Alcohol Derivatives

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(49), С. 20594 - 20599

Опубликована: Ноя. 30, 2020

A dual platform for forging sp2-sp3 and sp3-sp3 carbon bonds via catalytic β-scission of aliphatic alcohol derivatives with both aryl alkyl halides is disclosed. This protocol distinguished by its wide substrate scope broad applicability, even in the context late-stage functionalization.

Язык: Английский

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Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

European Journal of Organic Chemistry, Год журнала: 2021, Номер 2021(47), С. 6478 - 6510

Опубликована: Сен. 8, 2021

Abstract Current medicinal chemistry relies heavily on the quality of building blocks, i. e. reagents used to introduce chemical diversity into target molecules. The last decade witnessed an emergence many novel (or well‐overlooked old) chemotypes for drug discovery, which is related adapting new synthetic methodologies, designing sp 3 ‐enriched bioisosteres, paying attention previously underrated even unwanted) structural motifs, or combination thereof. In this review with 532 references, a survey selected that emerged recently in provided, focus synthesis corresponding blocks. Thus, saturated (hetero)aliphatic boronates, sulfonyl fluorides, sulfinates, non‐classical benzene isosteres, bicyclic morpholine/piperidine/piperazine analogs, as well gem ‐difluorinated cycloalkanes (as example emerging fluorinated motifs) are discussed.

Язык: Английский

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Boryl Radical Addition to Multiple Bonds in Organic Synthesis

European Journal of Organic Chemistry, Год журнала: 2019, Номер 2019(37), С. 6308 - 6319

Опубликована: Авг. 9, 2019

Boryl radicals have recently contributed to the development of organoboron chemistry, but synthetic application boryl is still limited compared with other radical species. The recent new reagents and catalytic systems has expanded practicality in it enabled addition reactions multiple bonds such as alkenes, alkynes, carbonyl groups their derivatives. additions can create not only novel compounds also unusual chemical transformations. This review summarizes developed radicals, which are roughly categorized by strategy for formation radicals: (1) B–H bond cleavage (2) B–B cleavage. Also, reaction mechanism outlined order understand design concept each reaction.

Язык: Английский

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