Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1875 - 1924

Опубликована: Авг. 6, 2021

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration aliphatic C–H bonds. In this manifold, photocatalyst (PCHAT) exploits energy photon to trigger homolytic cleavage such bonds in organic compounds. Selective bond may achieved by judicious abstractor (key parameters are electronic character and molecular structure), as well reaction additives. Different classes PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, metal-oxo porphyrin tris(amino)cyclopropenium radical dication. The processes (mainly C–C formation) most cases carried out under mild conditions with help visible light. aim review is offer comprehensive survey synthetic applications d-HAT.

Язык: Английский

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Radical C(sp3)–H functionalization and cross-coupling reactions

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(6), С. 405 - 427

Опубликована: Май 17, 2022

Язык: Английский

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Iron-Catalyzed C(Sp³)–H Borylation, Thiolation, and Sulfinylation Enabled by Photoinduced Ligand-to-Metal Charge Transfer

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(13), С. 7600 - 7611

Опубликована: Март 23, 2023

Catalytic C(sp3)-H functionalization has provided enormous opportunities to construct organic molecules, facilitating the derivatization of complex pharmaceutical compounds. Within this framework, direct hydrogen atom transfer (HAT) photocatalysis becomes an appealing approach goal. However, viable substrates utilized in these protocols are limited, and site selectivity shows preference activated thermodynamically favored bonds. Herein, we describe development undirected iron-catalyzed borylation, thiolation, sulfinylation reactions enabled by photoinduced ligand-to-metal charge (LMCT) process. These exhibit remarkably broad substrate scope (>150 examples total), most importantly, all three show unconventional regioselectivity, with occurrence preferentially at distal methyl position. The procedures operationally simple readily scalable provide access high-value products from hydrocarbons one step. Mechanistic studies control experiments indicate that afforded is not only relevant HAT species but also largely affected use boron- sulfone-based radical acceptors.

Язык: Английский

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Electronic control over site-selectivity in hydrogen atom transfer (HAT) based C(sp³)–H functionalization promoted by electrophilic reagents

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2171 - 2223

Опубликована: Янв. 1, 2022

Leveraging on electronic effects in both the substrate and HAT reagent, site-selectivity can be implemented C(sp 3 )–H bond functionalization.

Язык: Английский

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Functional group divergence and the structural basis of acridine photocatalysis revealed by direct decarboxysulfonylation

Chemical Science, Год журнала: 2022, Номер 13(14), С. 4170 - 4179

Опубликована: Янв. 1, 2022

The reactivity of the sulfonyl group varies dramatically from nucleophilic sulfinates through chemically robust sulfones to electrophilic halides-a feature that has been used extensively in medicinal chemistry, synthesis, and materials science, especially as bioisosteric replacements structural analogs carboxylic acids other carbonyls. Despite great synthetic potential functional interconversions, a method can convert directly sulfones, halides remained out reach. We report herein development photocatalytic system for first time enables direct decarboxylative conversion sulfinates, well chlorides fluorides one step multicomponent fashion. A mechanistic study prompted by new revealed key features acridine photocatalysts facilitate transformations provided an informative predictive multivariate linear regression model quantitatively relates with activity.

Язык: Английский

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Advances in the construction of diverse SuFEx linkers

National Science Review, Год журнала: 2023, Номер 10(6)

Опубликована: Апрель 29, 2023

Abstract Sulfur fluoride exchange (SuFEx), a new generation of click chemistry, was first presented by Sharpless, Dong and co-workers in 2014. Owing to the high stability yet efficient reactivity SVI–F bond, SuFEx has found widespread applications organic synthesis, materials science, chemical biology drug discovery. A diverse collection linkers emerged, involving gaseous SO2F2 SOF4 hubs; SOF4-derived iminosulfur oxydifluorides; O-, N- C-attached sulfonyl fluorides sulfonimidoyl fluorides; novel sulfondiimidoyl fluorides. This review summarizes progress these connectors, with an emphasis on analysing advantages disadvantages synthetic strategies connectors based concept, it is expected be beneficial researchers rapidly correctly understand this field, thus inspiring further development chemistry.

Язык: Английский

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Radical approaches to C–S bonds

Nature Reviews Chemistry, Год журнала: 2023, Номер 7(8), С. 573 - 589

Опубликована: Июнь 21, 2023

Язык: Английский

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Nickel-catalysed enantioselective alkene dicarbofunctionalization enabled by photochemical aliphatic C–H bond activation

Nature Catalysis, Год журнала: 2024, Номер 7(6), С. 655 - 665

Опубликована: Апрель 29, 2024

Abstract The development of novel strategies to rapidly construct complex chiral molecules from readily available feedstocks is a long-term pursuit in the chemistry community. Radical-mediated alkene difunctionalizations represent an excellent platform towards this goal. However, asymmetric versions remain highly challenging, and more importantly, examples featuring simple hydrocarbons as reaction partners are elusive. Here we report three-component dicarbofunctionalization capitalizing on direct activation C( sp 3 )–H bonds through combination photocatalysed hydrogen atom transfer nickel catalysis. This protocol provides efficient for installing two vicinal carbon–carbon across alkenes atom-economic fashion, providing wide array high-value α-aryl/alkenyl carbonyls phosphonates, well 1,1-diarylalkanes ubiquitous alkane, ether alcohol feedstocks. method exhibits operational simplicity, broad substrate scope regioselectivity, chemoselectivity enantioselectivity. compatibility with bioactive motifs expedient synthesis pharmaceutically relevant highlight synthetic potential protocol.

Язык: Английский

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Recent advances of decatungstate photocatalyst in HAT process

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(13), С. 2523 - 2538

Опубликована: Янв. 1, 2024

The decatungstate anion (W

Язык: Английский

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Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay

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

Опубликована: Фев. 17, 2024

Abstract Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts metal reductant and the requirement installing directing group to suppress inherent β-H elimination bring great limitations this type reaction. We demonstrate herein that two different accessible via radical-anion relay Na 2 S O 4 as both sulfone-source. The together electron-shuttle catalyst crucial divert mechanistic pathway toward formation sulfone anion instead previously reported alkylmetal intermediates. Mechanistic studies allow identification carbon-centered radical sulfur-centered radical, which are in equilibrium capture or extrusion SO could be converted accelerated by iron catalysis, leading observed high chemoselectivity.

Язык: Английский

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