The first example of the bis-alkoxycarbonylation of acrylic esters and acrylic amides, leading to differently substituted 1,1,2-ethanetricarboxylate compounds and 2-carbamoylsuccinates respectively, is reported. The catalyst is formed in situ by mixing Pd(TFA)2 (TFA=trifluoroacetate) and the ligand bis(2,6- dimethylphenyl)butane-2,3-diimine. The reaction, that proceeds using p-benzoquinone as oxidant and ptoluenesulfonic acid as additive, has been applied to variously substituted electron-poor alkenes, employing different alcohols as nucleophiles, under very mild reaction conditions (4 bar of carbon monoxide at 20°C). Remarkably, this catalytic system is able to promote the carbonylation of both the β- and the generally unreactive α-positions of acrylic esters and amides, allowing the formation of bis-alkoxycarbonylated products in good to excellent yields (up to 98%). The trend of reactivity, observed with the different electron-deficient olefins, has been rationalized on the basis of the proposed catalytic cycle and DFT calculations.

Bis-Alkoxycarbonylation of Acrylic Esters and Amides for the Synthesis of 2-Alkoxycarbonyl or 2-Carbamoyl Succinates / Olivieri, Diego; Tarroni, Riccardo; DELLA CA', Nicola; Mancuso, Raffaella; Gabriele, Bartolo; Spadoni, Gilberto; Carfagna, Carla. - In: ADVANCED SYNTHESIS & CATALYSIS. - ISSN 1615-4169. - 362:(2020), pp. 533-544. [10.1002/adsc.201900918]

Bis-Alkoxycarbonylation of Acrylic Esters and Amides for the Synthesis of 2-Alkoxycarbonyl or 2-Carbamoyl Succinates

Nicola Della Ca';
2020

Abstract

The first example of the bis-alkoxycarbonylation of acrylic esters and acrylic amides, leading to differently substituted 1,1,2-ethanetricarboxylate compounds and 2-carbamoylsuccinates respectively, is reported. The catalyst is formed in situ by mixing Pd(TFA)2 (TFA=trifluoroacetate) and the ligand bis(2,6- dimethylphenyl)butane-2,3-diimine. The reaction, that proceeds using p-benzoquinone as oxidant and ptoluenesulfonic acid as additive, has been applied to variously substituted electron-poor alkenes, employing different alcohols as nucleophiles, under very mild reaction conditions (4 bar of carbon monoxide at 20°C). Remarkably, this catalytic system is able to promote the carbonylation of both the β- and the generally unreactive α-positions of acrylic esters and amides, allowing the formation of bis-alkoxycarbonylated products in good to excellent yields (up to 98%). The trend of reactivity, observed with the different electron-deficient olefins, has been rationalized on the basis of the proposed catalytic cycle and DFT calculations.
Bis-Alkoxycarbonylation of Acrylic Esters and Amides for the Synthesis of 2-Alkoxycarbonyl or 2-Carbamoyl Succinates / Olivieri, Diego; Tarroni, Riccardo; DELLA CA', Nicola; Mancuso, Raffaella; Gabriele, Bartolo; Spadoni, Gilberto; Carfagna, Carla. - In: ADVANCED SYNTHESIS & CATALYSIS. - ISSN 1615-4169. - 362:(2020), pp. 533-544. [10.1002/adsc.201900918]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2866820
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