Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

Crespi, Stefano; Fagnoni, Maurizio

doi:10.1021/acs.chemrev.0c00278

Cited by 310 publications

(182 citation statements)

References 396 publications

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“…Considering those elements and based on our continuing interest in photoredox catalysis [12][13][14][15] and in photoredox/Ni dual catalysis, [16][17][18][19][20] we considered involving bis(catecholato)silicates in a photoredox/Ni-catalyzed vinylation reaction. 21 Indeed, thanks to their low oxidation potential (between 0.3 and 0.9 V vs SCE) bis(catecholato)silicates are known as efficient radical precursors.…”

Section: Cluster Synlettmentioning

confidence: 99%

Visible-Light-Mediated Z-Stereoselective Monoalkylation of β,β-Dichlorostyrenes by Photoredox/Nickel Dual Catalysis

Abdellaoui¹,

Millanvois²,

Levernier³

et al. 2021

Synlett

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Metal-catalyzed alkylation of 1,1-dihalovinyl moiety commonly suffers from both a lack of stereoselectivity and the overreaction leading to the dialkylation product. The methodology described herein features a new pathway to alkylate stereoselectively β,β-dichloro-styryl substrates to provide the (Z)-trisubstituted olefin only with fair to good yields. This cross-coupling reaction bears on the smooth and photo-induced formation of a C-centered radical that engages in a nickel-catalyzed organometallic cycle to form the key Csp2-Csp3 bond.

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Section: Cluster Synlettmentioning

confidence: 99%

Visible-Light-Mediated Z-Stereoselective Monoalkylation of β,β-Dichlorostyrenes by Photoredox/Nickel Dual Catalysis

Abdellaoui¹,

Millanvois²,

Levernier³

et al. 2021

Synlett

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“…In these reactions, substrates such as compounds with an -C(sp 3 )-H adjacent to heteroatom or simple alkanes have been employed to cause a facile HAT process and thus control the regioselectivity. There is still, however, a great demand for the development of a practical protocol using a readily available chemical as an alkyl radical source, [25][26][27] with the aim to construct complex ketones without redundant protection and deprotection process. The carboxylic acids could realize a synthetase-catalyzed formal decarboxylative acylation by transfer of an acyl group from coenzyme A (CoA) activated thioesters to deliver a chain-extended ketone 28 (Scheme 1a).…”

Section: Introductionmentioning

confidence: 99%

Decarboxylative Acylation of Carboxylic Acids: Reaction Investigation and Mechanistic Study

Han

Xia

et al. 2022

CCS Chem

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Ketones serve as one of the most critical building blocks in organic synthesis, involving in numerous functional group transformations. Herein, we report an unprecedented photoredox/nickel metallaphotoredox-catalyzed decarboxylative acylation of common aliphatic acids with readily available aromatic and aliphatic thioesters. A wide range of structural diverse unsymmetrical arylalkyl and dialkyl ketones have been constructed in yields of up to 98% with this strategy. The protocol has excellent reaction selectivity and functional group compatibility, representing a significant step forward in ketone synthesis. The one-pot decarboxylative acylation at the gram scale from two different carboxylic acids and the late-stage application for the synthesis of complex ketones shows its synthetic robustness. Both mechanistic experiments and DFT calculations suggest that the decarboxylative acylation reaction tends to operate via an underdeveloped Ni(I)−Ni(II)−Ni(I)−Ni(III)-Ni(I) catalytic cycle.

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“…Most of the non‐metallic elements are well represented in radical chemistry, with functional groups based on N, [6] O, [7] S, [8] Se [9] and the halogens all used to generate carbon‐centered radicals [10] . In contrast, the radical chemistry of phosphorus remains relatively underdeveloped.…”

Section: Introductionmentioning

confidence: 99%

Phosphorus Compounds as Precursors and Catalysts for Radical C−C Bond‐Forming Reactions

Maddigan-Wyatt

Hooper

2021

Adv Synth Catal

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The photochemistry of organophosphorus compounds and their reactions with carbon‐centred radicals was studied from the 1950s to the 70s, but has not been well exploited in synthetic chemistry until very recently. This review discusses the various modes of reactivity that phosphorus compounds display in radical C−C bond forming reactions, including the role of phosphonium salts as radical precursors, phosphines and phosphites as deoxygenating agents from oxygen‐centred radicals and phosphines in electron‐ and charge‐transfer chemistry. We also highlight the potential that these processes have in the future development of new reactions and cascade processes.

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Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

Cited by 310 publications

References 396 publications

Visible-Light-Mediated Z-Stereoselective Monoalkylation of β,β-Dichlorostyrenes by Photoredox/Nickel Dual Catalysis

Visible-Light-Mediated Z-Stereoselective Monoalkylation of β,β-Dichlorostyrenes by Photoredox/Nickel Dual Catalysis

Decarboxylative Acylation of Carboxylic Acids: Reaction Investigation and Mechanistic Study

Phosphorus Compounds as Precursors and Catalysts for Radical C−C Bond‐Forming Reactions

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