Carbonylative Suzuki–Miyaura couplings of sterically hindered aryl halides: synthesis of 2-aroylbenzoate derivatives

Ismael, Aya; Skrydstrup, Troels; Bayer, Annette

doi:10.1039/d0ob00044b

Cited by 12 publications

(3 citation statements)

References 45 publications

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“…Although extensive work has been done for this three-component C−C coupling, it remains limited to typical aryl systems. 18 Synthesis of biaryl ketones involving heterocyclic cores through carbonylation still remains an unexplored area, though most of the drug-like molecules with carbonyl units contain a heterocyclic moiety as the pharmacophore. 19 Structures containing isoquinoline and isoquinolone cores with C-4 aroyl groups, as shown in Figure 1, are topoisomerase inhibitors.…”

Section: Synthesis and Characterization Of [Pd(dmap) 2 (Oac) 2 ] (Com...mentioning

confidence: 99%

Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation

Halder,

Iqubal,

Mondal

et al. 2023

J. Org. Chem.

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A phosphine-free, efficient protocol for aminocarbonylation and carbonylative Suzuki–Miyaura coupling has been developed using a novel palladium complex, [PdII(DMAP)2(OAc)2]. The complex was successfully synthesized using a stoichiometric reaction between PdII(OAc)2 and DMAP in acetone at room temperature and characterized using single-crystal X-ray analysis. Only 5 mol % catalyst loading was sufficient for effective carbonylative transformations. “Chloroform-COware” chemistry was utilized for safe and facile insertion of the carbonyl unit using chloroform as an inexpensive CO source in a two-chamber setup. Various value-added pharmaceutically relevant compounds such as CX-516, CX-546, and farampator were synthesized using the technique. Furthermore, the commercially designed COware was engineered to COware-RB setup for sequential one-pot synthesis of indenoisoquinolines (topoisomerase I inhibitors).

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Section: Synthesis and Characterization Of [Pd(dmap) 2 (Oac) 2 ] (Com...mentioning

confidence: 99%

Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation

Halder,

Iqubal,

Mondal

et al. 2023

J. Org. Chem.

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“…Its wider application enabled easier data extraction in this study. We identified 75 journal articles, which included a total of 97 individual reactions, from which good quality data could be extracted and analyzed. ,,,,− The data shows a split between common mol % choices, 0–1 and 4–5 mol %, having ppm values up to 1000 ppm. It also shows that, from these selected papers, lower mol % values are preferred with ca.…”

Section: Suzuki–miyaura Cross-couplingmentioning

confidence: 99%

Pd-Catalyzed Cross-Couplings: On the Importance of the Catalyst Quantity Descriptors, mol % and ppm

Horbaczewskyj

Fairlamb

2022

Org. Process Res. Dev.

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This Review examines parts per million (ppm) palladium concentrations in catalytic cross-coupling reactions and their relationship with mole percentage (mol %). Most studies in catalytic cross-coupling chemistry have historically focused on the concentration ratio between (pre)catalyst and the limiting reagent (substrate), expressed as mol %. Several recent papers have outlined the use of “ppm level” palladium as an alternative means of describing catalytic cross-coupling reaction systems. This led us to delve deeper into the literature to assess whether “ppm level” palladium is a practically useful descriptor of catalyst quantities in palladium-catalyzed cross-coupling reactions. Indeed, we conjectured that many reactions could, unknowingly, have employed low “ppm levels” of palladium (pre)catalyst, and generally, what would the spread of ppm palladium look like across a selection of studies reported across the vast array of the cross-coupling chemistry literature. In a few selected examples, we have examined other metal catalyst systems for comparison with palladium.

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“…Renewable solvents have proven to be suitable for a variety of transformations including classical condensation reactions and transition-metal (TM)-catalyzed cross-couplings. − However, the use of renewable solvents as reaction media for carbonylative couplings with CO remain largely unexplored. , The fact that the Pd-catalyzed carbonylations have found numerous applications in modern drug discovery and isotopic labeling of pharmaceuticals 10d,e,g makes the development of renewable methodologies for carbonylations a task of great significance. This work describes the use of newly introduced biomass-derived solvents (acetal, dimethyl isosorbide, γ-terpinene, α-pinene, eucalyptol, and rose oxide, Figure ) and previously studied renewable solvents (2MeTHF, GVL, limonene, p -cymene, DMC, DEC, ethylene carbonate (EC), propylene carbonate (PC), methylal and diethoxymethane (ethylal), Figure ) for Pd-catalyzed carbonylations.…”

Section: Introductionmentioning

confidence: 99%

Renewable Solvents for Palladium-Catalyzed Carbonylation Reactions

Ismael

Gevorgyan

Skrydstrup

et al. 2020

Org. Process Res. Dev.

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Solvents constitute the largest component for many chemical processes and substitution of nonrenewable solvents is a longstanding goal for green chemistry. Here, we show that Pd-catalyzed carbonylative couplings, such as carbonylative cross-couplings, aminocarbonylations, and alkoxycarbonylations, can be successfully realized using renewable solvents. The present research covers not only well-established renewable solvents, such as 2-methyltetrahydrofuran (2MeTHF), limonene, and dimethyl carbonate, but also recently introduced biomass-derived 1,1-diethoxyethane, isosorbide dimethyl ether, eucalyptol, rose oxide, γ-terpinene, and α-pinene. The carbonylative coupling of boronic acids and aryl bromides works well in limonene. Aminocarbonylation gave excellent results in dimethyl carbonate, α-pinene, and limonene, while alkoxycarbonylation was successful in 2MeTHF, α-pinene, γ-terpinene, and dimethyl carbonate. The developed methods based on renewable solvents can be used for the synthesis of commercial drug Trimetozine and an analogue of Itopride.

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Carbonylative Suzuki–Miyaura couplings of sterically hindered aryl halides: synthesis of 2-aroylbenzoate derivatives

Abstract: A new protocol for carbonylative coupling of sterically hindered aryl bromides with boronic acids featuring slow addition of the boronic acid as a strategy to suppress unwanted non-carbonylative couplings for sterically hindered aryl bromides.

Cited by 12 publications

References 45 publications

Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation

Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation

Pd-Catalyzed Cross-Couplings: On the Importance of the Catalyst Quantity Descriptors, mol % and ppm

Renewable Solvents for Palladium-Catalyzed Carbonylation Reactions

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