Palladium-catalysed synthesis of the cinnamic methyl ester from styrene, carbon monoxide and methanol

Cometti, G.; Chiusoli, Gian Paolo

doi:10.1016/s0022-328x(00)82840-5

Cited by 34 publications

(6 citation statements)

References 7 publications

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“…7 To the best of our knowledge, the selective synthesis of methyl cinnamate from styrene, CO and MeOH has been reported previously only with unmodified palladium catalysts based on PdCl 2 and complex re-oxidizing systems (CuCl 2 /Cu(OAc) 2 /Mn(OAc) 2 (OAc Ϫ = OCOCH 3 Ϫ ); 8 CuCl 2 /Na(OAc)/MgCl 2 ). 9 In contrast, phosphine-modified palladium() catalysts have been reported to produce methyl cinnamate via Heck-type methoxycarbonylation of β-bromostyrene. 10 In this work, we describe new diphosphine-modified palladium systems that are able to catalyse the oxidative carbonylation of styrene in MeOH yielding selectively either methyl cinnamate or dimethyl phenylsuccinate depending on subtle variations in the ligand structure as well as in the reaction conditions.…”

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confidence: 99%

Novel diphosphine-modified palladium catalysts for oxidative carbonylation of styrene to methyl cinnamate †

Bianchini

Mantovani

Meli

et al. 2001

J. Chem. Soc., Dalton Trans.

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confidence: 99%

Novel diphosphine-modified palladium catalysts for oxidative carbonylation of styrene to methyl cinnamate †

Bianchini

Mantovani

Meli

et al. 2001

J. Chem. Soc., Dalton Trans.

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“…The formation of diester is minimized by working at a carbon monoxide partial pressure of only 0.2 bar (CO/N2 mixture). (284) Scheme 7.1S NaOAc 6:,…”

Section: R~or'mentioning

confidence: 99%

Carbonylation

Colquhoun¹,

Thompson²,

Twigg³

1991

236

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“…52 On the other hand, higher CO pressure, in combination with certain ligands, led to the formation of the dicarbonylated products. 25,52 Bianchini et al successfully controlled the selectivity of the methoxycarbonylation of styrene by steering it either toward methylcinnamate or to dimethyl phenyl succinate by employing palladium precursors with various phosphine ligands. 22 In light of the numerous conditions published to date, we set out to decipher the competition between the two mechanisms.…”

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confidence: 99%

Competing Mechanisms in Palladium-Catalyzed Alkoxycarbonylation of Styrene

Mehara,

Anania,

Kočovský

et al. 2024

ACS Catal.

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Palladium-catalyzed carbonylation is a versatile method for the synthesis of various aldehydes, esters, lactones, or lactams. Alkoxycarbonylation of alkenes with carbon monoxide and alcohol produces either saturated or unsaturated esters as a result of two distinct catalytic cycles. The existing literature presents an inconsistent account of the procedures favoring oxidative carbonylation products. In this study, we have monitored the intermediates featured in both catalytic cycles of the methoxycarbonylation of styrene PhCH�CH 2 as a model substrate, including all short-lived intermediates, using mass spectrometry. Comparing the reaction kinetics of the intermediates in both cycles in the same reaction mixture shows that the reaction proceeding via alkoxy intermediate [Pd II ]-OR, which gives rise to the unsaturated product PhCH�CHCO 2 Me, is faster. However, with an advancing reaction time, the gradually changing reaction conditions begin to favor the catalytic cycle dominated by palladium hydride [Pd II ]-H and alkyl intermediates, affording the saturated products PhCH 2 CH 2 CO 2 Me and PhCH(CO 2 Me)CH 3 preferentially. The role of the oxidant proved to be crucial: using p-benzoquinone results in a gradual decrease of the pH during the reaction, swaying the system from oxidative conditions toward the palladium hydride cycle. By contrast, copper(II) acetate as an oxidant guards the pH within the 5−7 range and facilitates the formation of the alkoxy palladium complex [Pd II ]-OR, which favors the oxidative reaction producing PhCH�CHCO 2 Me with high selectivity. Hence, it is the oxidant, rather than the catalyst, that controls the reaction outcome by a mechanistic switch. Unraveling these principles broadens the scope for developing alkoxycarbonylation reactions and their application in organic synthesis.

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Palladium-catalysed synthesis of the cinnamic methyl ester from styrene, carbon monoxide and methanol

Cited by 34 publications

References 7 publications

Novel diphosphine-modified palladium catalysts for oxidative carbonylation of styrene to methyl cinnamate †

Novel diphosphine-modified palladium catalysts for oxidative carbonylation of styrene to methyl cinnamate †

Carbonylation

Competing Mechanisms in Palladium-Catalyzed Alkoxycarbonylation of Styrene

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