Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

Monsigny, Louis; Doche, Floriane; Besset, Tatiana

doi:10.3762/bjoc.19.35

Cited by 8 publications

(2 citation statements)

References 215 publications

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“…As a result, a few publications have reported transition metal-catalyzed thiocyanation of CÀ H bonds, [30][31][32][33][34][35][36][37] using directing groups or activated positions to control the selectivity. For example, Besset et al described the palladium-catalyzed directed thiocyanation of acrylamides and 2-arylpyridines by Pdcatalyzed C(sp 2 )À H bond activation, [38,39] and the group of Xiao and Zhu reported a C(sp 3 )À H bond thiocyanation reaction of 2aminofurans under palladium(II) catalysis.…”

Section: Introductionmentioning

confidence: 99%

C‐Centered radical intermediates for C(sp³)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates

Buttard,

Vigier,

Lebel

et al. 2024

Eur J Org Chem

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Organic thiocyanates are an important class of compounds because they are present in several bioactive molecules and can be used as key synthetic intermediates to access biorelevant sulfur‐containing scaffolds. Although the chemistry of organothiocyanates has been studied for decades, a recent resurgence of interest in the field has led to major advances in the synthesis of new molecules bearing a thiocyanate moiety. An emerging and powerful strategy consists in the selective functionalization of C(sp3)‐H bonds through the formation of a key C‐centered radical intermediate. This review highlights the recent work that has been reported to access novel alkylthiocyanate scaffolds through this promising approach.

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Section: Introductionmentioning

confidence: 99%

C‐Centered radical intermediates for C(sp³)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates

Buttard,

Vigier,

Lebel

et al. 2024

Eur J Org Chem

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“…Over the last few years, emergent fluorinated groups have offered efficient and interesting alternatives to the classical fluorine atom and trifluoromethyl moiety thanks to their unique physicochemical properties . Among them, the trifluoromethylthiolated group has proven to be a high-added-value fluorinated residue thanks to its electron-withdrawing character and its high lipophilicity . Therefore, the bourgeoning developments related to this fluorinated moiety require the discovery of novel and more effective synthetic strategies for its installation in the widely available, and biologically and chemically important, small molecules and heterocycles …”

Section: Introductionmentioning

confidence: 99%

Photocatalytic α-Trifluoromethylthiolation of N-Acyl Amines

Doche,

Poisson,

Besset

2023

ACS Catal.

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A photocatalytic approach for the C(sp 3 )−H trifluoromethylthiolation of amides under mild reaction conditions is reported. We have developed a protocol that tolerates a large range of functional groups and allows the functionalization of aromatic and aliphatic amides in high yields (26 examples, up to 83% yield) by using a low catalytic loading of an organophotocatalyst. With this approach, the synthesis of original fluorinated acyclic thioaminals is successfully achieved. Detailed mechanistic studies are conducted and enable deciphering an oxidative quenching catalytic cycle via a proton-coupled electron transfer (PCET), allowing the formation of a primary radical at the α-position of the nitrogen.

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Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group

Dupommier,

Vuagnat,

Rzayev

et al. 2024

Angewandte Chemie

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Site‐selective ortho/ipso C‐H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up to 97% yields). To ensure the excellent regioselectivity of the process while keeping high efficiency, an original strategy based on a “C‐H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized arenes were first regioselectively converted into the corresponding thianthrenium salts. Then, a palladium‐catalyzed, norbornene (NBE)‐mediated process allowed the synthesis of ipso‐olefinated/ortho‐alkylated polyfunctionalized arenes using a thianthrene as a leaving group (revisited Catellani reaction). Pleasingly, using a commercially available norbornene (NBE) and a unique catalytic system, synthetic challenges known for the Catellani reaction with aryl iodides were smoothly and successfully tackled with the “thianthrenium” approach. The protocol was robust (gram‐scale reaction) and was widely applied to the two‐fold functionalization of various arenes including bio‐active compounds. Moreover, a panel of olefins and alkyl halides as coupling partners was suitable. Pleasingly, the “thianthrenium” strategy was successfully further applied to the incorporation of other groups at the ipso (CN/alkyl/H, aryl) and ortho (alkyl, aryl, amine, thiol) positions, showcasing the generality of the process.

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Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

Cited by 8 publications

References 215 publications

C‐Centered radical intermediates for C(sp³)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates

C‐Centered radical intermediates for C(sp³)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates

Photocatalytic α-Trifluoromethylthiolation of N-Acyl Amines

Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group

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Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

Cited by 8 publications

References 215 publications

C‐Centered radical intermediates for C(sp3)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates

C‐Centered radical intermediates for C(sp3)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates

Photocatalytic α-Trifluoromethylthiolation of N-Acyl Amines

Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group

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C‐Centered radical intermediates for C(sp³)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates

C‐Centered radical intermediates for C(sp³)‐H bonds functionalization: An emerging approach towards alkyl thiocyanates