Enantioconvergent Fukuyama Cross‐Coupling of Racemic Benzylic Organozinc Reagents

Oost, Rik; Misale, Antonio; Maulide, Nuno

doi:10.1002/ange.201600597

Cited by 37 publications

(2 citation statements)

References 44 publications

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“…Although numerous enantioselective approaches for preparing quaternary α-aryl ketones have been reported 3 – 5 , asymmetric methods to access more commonly encountered tertiary variants remain limited presumably owing to the lability of tertiary stereocenters 6 . Nevertheless, transition-metal catalyzed asymmetric couplings of aryl organometallic reagents with α-bromo ketones 7 – 9 , benzylic zinc reagents with thioesters 10 , benzylic chlorides with acid chlorides under reductive conditons 11 , and aryl alkenes with activated carboxylic acids in the presence of a hydrosilane 12 , 13 have been disclosed in seminal studies by Fu, Maulide, Reisman, and Buchwald, respectively (Fig. 1a ).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric benzylic C(sp3)−H acylation via dual nickel and photoredox catalysis

Huan

Shu

et al. 2021

Nat Commun

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Asymmetric C(sp3)−H functionalization is a persistent challenge in organic synthesis. Here, we report an asymmetric benzylic C−H acylation of alkylarenes employing carboxylic acids as acyl surrogates for the synthesis of α-aryl ketones via nickel and photoredox dual catalysis. This mild yet straightforward protocol transforms a diverse array of feedstock carboxylic acids and simple alkyl benzenes into highly valuable α-aryl ketones with high enantioselectivities. The utility of this method is showcased in the gram-scale synthesis and late-stage modification of medicinally relevant molecules. Mechanistic studies suggest a photocatalytically generated bromine radical can perform benzylic C−H cleavage to activate alkylarenes as nucleophilic coupling partners which can then engage in a nickel-catalyzed asymmetric acyl cross-coupling reaction. This bromine-radical-mediated C−H activation strategy can be also applied to the enantioselective coupling of alkylarenes with chloroformate for the synthesis of chiral α-aryl esters.

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Section: Introductionmentioning

confidence: 99%

Asymmetric benzylic C(sp3)−H acylation via dual nickel and photoredox catalysis

Huan

Shu

et al. 2021

Nat Commun

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“…Raman spectroscopy attributed to the W=O and the W−Cl bond vibrations, respectively. reaction, [112][113][114][115] Negishi reaction, [116][117][118] Fukuyama reaction, [119][120][121][122][123][124] etc. it is still to explore catalytic borylation.…”

Section: Scheme 7 Copolymerization Of Ethylene/nbe Bymentioning

confidence: 99%

Recent Advances of Imidazolin-2-iminato in Transition Metal Chemistry

raja¹,

Revathi²,

Ghatak³

2020

Eng. Sci.

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Visible Light Assisted Radical‐Polar/Polar‐Radical Crossover Reactions in Organic Synthesis

2021

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Chemists are generally familiar with polar reactions and radical reactions, in comparison, are underdeveloped. In the last few years, however, the novel concept of amalgamation of the above two in the form of radical‐polar crossover (RPCO) and polar‐radical crossover (PRCO) reactions has emerged as a valuable and powerful tool. This methodology tends to bridge the gap between the two as well as overcomes limitations of both radical and traditional polar chemistry. By bringing together the unorthodox chemistry of radicals with orthodox carbocations and carbanions, the green quotient of such reactions is significantly improved. The development and shaping up of this area in the last few years in the form of synthetically important transformations is summarised in this review.

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Enantioconvergent Fukuyama Cross‐Coupling of Racemic Benzylic Organozinc Reagents

Cited by 37 publications

References 44 publications

Asymmetric benzylic C(sp3)−H acylation via dual nickel and photoredox catalysis

Asymmetric benzylic C(sp3)−H acylation via dual nickel and photoredox catalysis

Recent Advances of Imidazolin-2-iminato in Transition Metal Chemistry

Visible Light Assisted Radical‐Polar/Polar‐Radical Crossover Reactions in Organic Synthesis

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