Copper-Catalyzed Alkoxycarbonylation of Alkyl Iodides for the Synthesis of Aliphatic Esters: Hydrogen Makes the Difference

Geng, Hui‐Qing; Wu, Xiao‐Feng

doi:10.1021/acs.orglett.1c03071

Cited by 15 publications

(11 citation statements)

References 29 publications

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“…15 Irradiating the reaction with blue LED light (390 nm) at room temperature resulted in 96% conversion to anhydride 2a (entry 2). Although Cu-catalyzed carbonylation reactions have produced carboxylic acid derivatives such as esters, 16 amides, [17][18][19][20][21] and other acyl-X compounds, 22,23 there is no precedent for anhydride formation. Similar results were observed with NaOH in place of K2CO3 (entry 3), but no 2a was observed when using alkoxide bases (see Table S2).…”

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confidence: 99%

Light-mediated synthesis of aliphatic anhydrides by Cu-catalyzed carbonylation of alkyl halides

Tung

Mankad

2022

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Acid anhydrides are valuable in the chemical industry for their role in synthesizing polymers, pharmaceuticals, and other commodities, but their syntheses often involve multiple steps with precious metal catalysts. The simplest anhydride, acetic anhydride, is currently produced by two Rh-catalyzed carbonylation reactions on bulk scale for its use in synthesizing products ranging from aspirin to cellulose acetate. Here, we report a light-mediated, Cu-catalyzed process for producing aliphatic, symmetric acid anhydrides directly by carbonylation of alkyl (pseudo-)halides in a single step without any precious metal additives. The transformation requires only simple Cu salts and abundant bases to proceed, maintains high efficiency and selectivity upon scale up, and operates by radical mechanism with several beneficial features. This discovery will enable engineering of bulk processes for producing commodity anhydrides efficiently and sustainably.

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confidence: 99%

Light-mediated synthesis of aliphatic anhydrides by Cu-catalyzed carbonylation of alkyl halides

Tung

Mankad

2022

Preprint

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“…In 2021, Geng and Wu reported a copper-catalyzed alkoxycarbonylation transformation of unactivated alkyl iodides in the presence of syngas (CO + H 2 ). 23 NaO t Bu acts as both a nucleophile and a base. With 10 bar CO and 20 bar H 2 , various alkyl iodides were converted into the corresponding tert -butyl esters in 59–98% yields (Scheme 11).…”

Section: Copper-catalyzed Carbonylation To Synthesize Estersmentioning

confidence: 99%

Recent advances in Cu-catalyzed carbonylation with CO

et al. 2022

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“…In addition to the widely used alkoxycarbonylation of aryl halides and iodoalkenes [ 17 , 18 , 19 , 20 , 21 ], and their synthetic surrogates (aryl triflates and enol triflates), aryloxycarbonylation has become a well-established and long-applied homogeneous catalytic reaction [ 22 , 23 , 24 , 25 , 26 , 27 , 28 ]. While the application of alcohols and phenols as O -nucleophiles in transition metal-catalyzed carbonylations is widely known and can be considered as a general synthetic tool, azidocarbonylation is still a recent discovery, dating back only a few years [ 29 , 30 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

2022

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Novel, elongated, resorcine[4]arene-based cavitands were synthesized via various consecutive reaction steps, including homogeneous catalytic aryloxy- and azidocarbonylation processes. The effects of carbon monoxide pressure and temperature on the conversion were examined in aryloxycarbonylation. It was revealed that a reaction temperature of 100 °C is required to achieve complete conversion both with monodentate (PPh3) and bidentate (Xantphos) phosphines at different carbon monoxide pressures (1–40 bar). Using ten different phenols as O-nucleophiles, partial hydrolysis of the esters to the corresponding carboxylic acids took place—i.e., 58–90% chemoselectivities toward esters were obtained. Moreover, the influences of temperature, reaction time and the catalyst ratio on the selectivity and conversion were described in the case of azidocarbonylation reaction. The formation of the acyl azide with high chemoselevtivity can be achieved at room temperature only. The higher reaction temperatures (50 °C) and higher catalyst loadings favor the formation of the primary amide. The characterization of the target compounds (esters and acyl azides) was carried out by IR and 1H and 13C NMR. The discussion of the influences of various parameters is based on in situ NMR investigations.

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Copper-Catalyzed Alkoxycarbonylation of Alkyl Iodides for the Synthesis of Aliphatic Esters: Hydrogen Makes the Difference

Cited by 15 publications

References 29 publications

Light-mediated synthesis of aliphatic anhydrides by Cu-catalyzed carbonylation of alkyl halides

Light-mediated synthesis of aliphatic anhydrides by Cu-catalyzed carbonylation of alkyl halides

Recent advances in Cu-catalyzed carbonylation with CO

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

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