Copper(1) catalysed aromatic nucleophilic substitution: A mechanistic and synthetic comparison with the SRN1 reaction

Bowman, W. Russell; Heaney, H.; Smith, P.

doi:10.1016/s0040-4039(01)81695-6

Cited by 72 publications

(28 citation statements)

References 13 publications

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“…The intervention of oxidative addition-reductive elimination mechanism in Ullmann condensation was first proposed by Cohen 23 in 1974 and substantiated by follow-up studies from others, 19,20,24 indicating Cu(I) and Cu(III) are intermediates in this type of reactions. The exceptionally high catalytic activity of copper(I) thiophene-2-carboxylate in Ullmann type nucleophilic substitution reactions has been ascribed to the stabilization of the Cu(III) complex formed in the oxidative addition step thereby driving the equilibrium to the forward direction.…”

Section: Proposed Mechanismmentioning

confidence: 84%

“…Elimination addition mechanism via an aryne intermediate can also be ruled out as there is no scope for formation of any hetero aryne intermediate in the case of 1b and 1e. 18 20 we observed that part of sodium bisulphite was destroyed by these agents leading to incomplete reaction but the desired product was also formed. Interestingly, we found that p-dinitro benzene could not be used as radical scavenger in this reaction, as it was getting reduced to form p-nitro aniline under the reaction conditions.…”

Section: Proposed Mechanismmentioning

confidence: 94%

“…al investigated the mechanism with respect to radical pathway and their experimental observations led to the inference that no aryl radicals are produced under copper(I) catalyzed conditions. 20 Further in contrast to the 3-bromo and 5-bromo isomers, the cuprous chloride catalyzed nucleophilic substitution reaction of 4-bromo thiophene-2-carboxyli acid 1c with sodium bisulphite, was significantly very slow. The observed reactivity 1b > 1d >> 1c cannot be accounted for by S RN 1 mechanism.…”

Section: Proposed Mechanismmentioning

confidence: 99%

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Ortho‐carboxylate Effects in Copper‐mediated Nucleophilic Substitution of Halothiophenecarboxylic Acids and Halobenzoic Acids with Sodium Bisulphite

Ramaswamy

Mohanasundaram²,

Murugesan

et al. 2011

J Chinese Chemical Soc

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Ortho-carboxylate effects in Ullmann type nucleophilic substitution reactions were found to be much more pronounced as compared to those of other substituent and steric factors. In this study, we propose an ortho halogen assisted intramolecular oxidative addition-reductive elimination mechanism that fits our experimental observations. Experimental data has been generated with halothiophenecarboxylic acids and halobenzoic acids by performing copper-mediated nucleophilic substitution with scant referred sodium bisulphite as nucleophile under aqueous conditions. The novel mechanism was used to establish a new and improved process for preparation of monopotassium salts of 3-sulphothiophene-2-carboxylic acid, 2-sulphobenzoic acid, and 5-sulphothiophene-2-carboxylic acid. These monopotassium salts are critical intermediates and building blocks in the preparation of several therapeutically valuable drugs. The differences in reactivity between the halogens, chlorine and bromine was utilized to prepare aryl ethers including 2-acetyl-3-phenoxythiophene and 2-acetyl-3-(m-tolyloxy)thiophene that have not been reported in literature so far.

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Section: Proposed Mechanismmentioning

confidence: 84%

Section: Proposed Mechanismmentioning

confidence: 94%

Section: Proposed Mechanismmentioning

confidence: 99%

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Ortho‐carboxylate Effects in Copper‐mediated Nucleophilic Substitution of Halothiophenecarboxylic Acids and Halobenzoic Acids with Sodium Bisulphite

Ramaswamy

Mohanasundaram²,

Murugesan

et al. 2011

J Chinese Chemical Soc

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“…While most of the evidence collected so far has shown that the active catalyst is a ligand-copper(I)-nucleophile [(L)Cu I (Nu)] species, there is no such agreement on the way this catalyst activates the aryl halide (ArY, Y = Cl, Br and I). The most invoked routes are based on either one-electron redox processes through the radical intermediate Cu I /Cu II catalytic cycle namely Single Electron Transfer (SET) and Halogen Atom Transfer (HAT) [4,[39][40][41][42], or on two-electron redox processes via a Cu I /Cu III catalytic cycle like Oxidative Addition-Reductive Elimination (OA-RE) or σ-bond Metathesis (MET) (Scheme 1) [37,38,[43][44][45][46][47][48][49][50]. Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

et al. 2017

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Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH 2 ), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition-Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving Cu III intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.

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“…6 Hence there has been an obvious interest towards the development of synthetic methodologies for the synthesis of these compounds. The majority of the reported protocols involved transition metals like Pd, [7][8] Cu, [9][10][11][12] Ni, [13][14][15] and Fe [16][17][18] in the reaction of aryl halides or aryl boronic acids to form chalcogenides. But few transition metal-free procedures were also reported for the reaction of aryl diazonium salts and lithium, sodium and potassium salt of arene thiolate / selenolate/ tellurolate.…”

Section: Introductionmentioning

confidence: 99%

Transition metal- and solvent-free synthesis of unsymmetrical diaryl sulfides and selenides under ball-milling

Mukherjee¹,

Chatterjee²,

Ranu³

2015

Arkivoc

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A transition metal-and solvent-free procedure for the reaction of aryl diazonium tetrafluoroborates and thiols or selenols over alumina surface under ball-milling at ambient temperature, has been developed for the synthesis of unsymmetrical diaryl or aryl-alkyl sulfides and selenides. A wide range of functionalized diaryl or aryl-alkyl sulfides and selenides were obtained in high yields and high purity within a short reaction time (5-8 min.) by this protocol.

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Copper(1) catalysed aromatic nucleophilic substitution: A mechanistic and synthetic comparison with the SRN1 reaction

Cited by 72 publications

References 13 publications

Ortho‐carboxylate Effects in Copper‐mediated Nucleophilic Substitution of Halothiophenecarboxylic Acids and Halobenzoic Acids with Sodium Bisulphite

Ortho‐carboxylate Effects in Copper‐mediated Nucleophilic Substitution of Halothiophenecarboxylic Acids and Halobenzoic Acids with Sodium Bisulphite

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

Transition metal- and solvent-free synthesis of unsymmetrical diaryl sulfides and selenides under ball-milling

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