ChemInform Abstract: Mild Palladium‐Catalyzed Oxidative Direct ortho‐C—H Acylation of Anilides under Aqueous Conditions.

Szabo, F.; Daru, János; Simkó, Dániel Csaba; Nagy, Tibor; Stirling, András; Novàk, Zoltán

doi:10.1002/chin.201332079

Cited by 7 publications

(8 citation statements)

References 1 publication

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“…Second, an alternative reaction energy and barrier height are computed for the H 2 activation by a frustrated Lewis pair type catalyst (FLPO) 93 (see Figure 11 of ref ( 12 )). The third reaction involves a palladium catalyzed C–H bond activation 94 as depicted in Figure 12 of ref ( 12 ). The corresponding errors in reaction energies and barrier heights depicted in Figure 5 and gathered in Table S9 of the Supporting Information are excellent being in the range of −0.01 to 0.48 kJ/mol with the 10 –5 threshold.…”

Section: Resultsmentioning

confidence: 99%

Accurate Reduced-Cost CCSD(T) Energies: Parallel Implementation, Benchmarks, and Large-Scale Applications

Gyevi-Nagy

Kállay

Nagy

2021

J. Chem. Theory Comput.

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The accurate and systematically improvable frozen natural orbital (FNO) and natural auxiliary function (NAF) cost-reducing approaches are combined with our recent coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] implementations. Both of the closed- and open-shell FNO-CCSD(T) codes benefit from OpenMP parallelism, completely or partially integral-direct density-fitting algorithms, checkpointing, and hand-optimized, memory- and operation count effective implementations exploiting all permutational symmetries. The closed-shell CCSD(T) code requires negligible disk I/O and network bandwidth, is MPI/OpenMP parallel, and exhibits outstanding peak performance utilization of 50–70% up to hundreds of cores. Conservative FNO and NAF truncation thresholds benchmarked for challenging reaction, atomization, and ionization energies of both closed- and open-shell species are shown to maintain 1 kJ/mol accuracy against canonical CCSD(T) for systems of 31–43 atoms even with large basis sets. The cost reduction of up to an order of magnitude achieved extends the reach of FNO-CCSD(T) to systems of 50–75 atoms (up to 2124 atomic orbitals) with triple- and quadruple-ζ basis sets, which is unprecedented without local approximations. Consequently, a considerably larger portion of the chemical compound space can now be covered by the practically “gold standard” quality FNO-CCSD(T) method using affordable resources and about a week of wall time. Large-scale applications are presented for organocatalytic and transition-metal reactions as well as noncovalent interactions. Possible applications for benchmarking local CCSD(T) methods, as well as for the accuracy assessment or parametrization of less complete models, for example, density functional approximations or machine learning potentials, are also outlined.

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Section: Resultsmentioning

confidence: 99%

Accurate Reduced-Cost CCSD(T) Energies: Parallel Implementation, Benchmarks, and Large-Scale Applications

Gyevi-Nagy

Kállay

Nagy

2021

J. Chem. Theory Comput.

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“…Apart from pK a known in most cases only in water, these could be for instance PA 11 or H D 0 . 13 We believe that predicted pK a values from available software like e.g., MarvinSketch 19 provide a sufficient estimate. However, other acidity parameters in solvent of interest can provide more accurate results.…”

Section: Selection Of the Optimal Added Acidmentioning

confidence: 98%

C–H Functionalizations by Palladium Carboxylates: The Acid Effect

et al. 2019

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Finding optimal reaction conditions is usually complex, requires many experiments and is therefore demanding in terms of human, financial and environmental resources. This work provides a simple workflow for easier design of popular palladium catalyzed C-H functionalization reactions, where the active palladium catalysts contain carboxylate ligands. The key factor for optimizing reaction conditions is to find a balance between two opposing effects of the carboxylic acid in the reaction mixture; generation of more reactive palladium catalyst vs. deactivation of substrate by its protonation.

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“…Novak and coworkers have also published on Pd-catalyzed anilide C–H bond acylation with aldehydes under aqueous conditions, demonstrating an observable rate acceleration with the use of acid and the detergent sodium dodecyl sulfate (SDS). 28 In a subsequent paper the same group then developed a three-step one-pot procedure for the synthesis of 2-amino benzophenone derivatives via (1) protection or acylation of anilines, (2) Pd-catalyzed cross dehydrogenative coupling of aldehydes under aqueous conditions at ambient temperature, and (3) hydrolytic amide deprotection. 29 …”

Section: Aldehydesmentioning

confidence: 99%

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

2016

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The transition metal-catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functionality group compatibility and without the production of waste byproducts. Additionally, many transition metal-catalyzed C–H bond additions to polarized π-bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition metal catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds.

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ChemInform Abstract: Mild Palladium‐Catalyzed Oxidative Direct ortho‐C—H Acylation of Anilides under Aqueous Conditions.

Cited by 7 publications

References 1 publication

Accurate Reduced-Cost CCSD(T) Energies: Parallel Implementation, Benchmarks, and Large-Scale Applications

Accurate Reduced-Cost CCSD(T) Energies: Parallel Implementation, Benchmarks, and Large-Scale Applications

C–H Functionalizations by Palladium Carboxylates: The Acid Effect

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

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