Access to β‐Ketonitriles through Nickel‐Catalyzed Carbonylative Coupling of α‐Bromonitriles with Alkylzinc Reagents

Donslund, Aske S.; Neumann, Karoline T.; Corneliussen, Nicklas Pham; Grove, Ebbe Klit; Herbstritt, Domenique; Daasbjerg, Kim; Skrydstrup, Troels

doi:10.1002/chem.201902206

Cited by 46 publications

(16 citation statements)

References 40 publications

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“…Mechanistic pathways via two one-electron steps have been computationally evaluated in previous publications, mainly focusing on a variety of alkyl–alkyl coupling reactions. ,,,− Comparable mechanisms have been proposed for the carbonylation of alkyl iodides with palladium, where the single-electron transfer (SET) is initiated photocatalytically. The subsequent reaction steps are very similar to those proposed for nickel and considered for the system presented here. , The involvement of alkyl radicals generated by SET from the corresponding alkyl halides in Ni-catalyzed reactions has been suggested by different research groups. ,− However, to the best of our knowledge, an in-depth comparison between oxidative addition/reductive elimination and potential radical pathways has not been carried out yet. Additionally, the aim of our investigation was to evaluate the role of the ligand and LiI in order to identify the ideal ligands and additives for these reactions.…”

Section: Results and Discussionmentioning

confidence: 99%

Mechanistic Investigation of the Nickel-Catalyzed Carbonylation of Alcohols

Sabater¹,

Menche

Ghosh³

et al. 2020

Organometallics

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The carbonylation of alcohols represents a straightforward and atom-efficient methodology for the preparation of carboxylic acids. It is desirable to perform these reactions under precious metal-free and low-pressure conditions, with regioselectivity control. In this work, we present a detailed mechanistic study of a catalytic system based on NiI2, which can carbonylate benzylic alcohols in a highly regioselective manner to the corresponding branched carboxylic acids, core motifs for nonsteroidal drugs. The combination of catalytic amounts of nickel and iodide is crucial for efficient catalytic and regioselective conversion. Quantum-chemical computations were used to evaluate the underlying mechanistic processes. They revealed that a combination of two mechanisms is responsible for the observed reactivity and that the oxidative addition of alkyl halides to the Ni(0) species follows a radical oxidation pathway via two one-electron steps.

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Section: Results and Discussionmentioning

confidence: 99%

Mechanistic Investigation of the Nickel-Catalyzed Carbonylation of Alcohols

Sabater¹,

Menche

Ghosh³

et al. 2020

Organometallics

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“…Much to our delight, the yields of 3a could be further improved to 87% and 83% respectively, when amide-type pincer ligand (e.g. N-(pyridin-2-ylmethyl)picolinamide (L1) or N-(quinolin-8-yl)picolinamide (L2)) was used (entries 3-4), though they were seldom used as ligands in transition metal-catalyzed cross-coupling reactions [53][54][55][56] . This discovery encouraged us to synthesize two new sterically more hindered methylated derivatives L3 and L4 as ligands.…”

Section: Resultsmentioning

confidence: 99%

Nickel-Catalyzed Deaminative Sonogashira Coupling of Alkylpyridinium Salts Enabled by a New NN2 Pincer Ligand

Zhang

Jiao

et al. 2020

Preprint

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Alkynes are amongst the most valuable functional groups in organic chemistry and widely used in chemical biology, pharmacy, and materials science. However, the preparation of alkyl-substituted alkynes still remains elusive. Herein, a novel transformation is disclosed that enables the coupling of terminal alkynes with alkylpyridinium salts under Ni-catalysis. Key to the success of this coupling was the development of a new and readily accessible amide-type pincer ligand. This ligand allows naturally abundant alkyl amines as alkylating agents in Sonogashira reactions for the first time, and leads to diverse alkynes in excellent yields under mild conditions. Salient merits of this chemistry include broad substrates scope and functional group tolerance, gram-scale synthesis, one-pot transformation, versatile late-stage derivatizations as well as the use of inexpensive pre-catalyst and readily available substrates. The high efficiency and strong practicability bode well for the widespread applications of this strategy in constructing functional molecules, materials, and fine chemicals.

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“…The complexes 1 , 2 , 3 , 4 , 5 , and [Cp*IrCl 2 ] 2 were prepared according to the literature method. 2-(4-Benzyloxyphenyl) ethanol and N -benzyl-2-anilinoethanol were prepared according to the literature method. An aqueous dimethylamine solution (50%) and an aqueous methylamine solution (40%) are commercially available and were used as received.…”

Section: Methodsmentioning

confidence: 99%

“…The complexes 1, 15c 2, 20 were prepared according to the literature method. 2-(4-Benzyloxyphenyl) ethanol 23 and N-benzyl-2-anilinoethanol 24 were prepared Scheme 3. Investigation of N-Monomethylamination Using an Aqueous Methylamine Solution a a Reaction was carried out with primary alcohol (1.0 mmol), methylamine (6.0 mmol), catalyst 5 (1.0 mol %), and K 2 CO 3 %) at 120 °C for 40 h. Yields were determined by GC analysis.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Dimethylamination of Primary Alcohols Using a Homogeneous Iridium Catalyst: A Synthetic Method for N,N-Dimethylamine Derivatives

Jeong

Fujita

2021

J. Org. Chem.

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A new catalytic system for N,N-dimethylamination of primary alcohols using aqueous dimethylamine in the absence of additional organic solvents has been developed. The reaction proceeds via borrowing hydrogen processes, which are atom-efficient and environmentally benign. An iridium catalyst bearing an N-heterocyclic carbene (NHC) ligand exhibited high performance, without showing any deactivation under aqueous conditions. In addition, valuable N,Ndimethylamine derivatives, including biologically active and pharmaceutical molecules, were synthesized. The practical application of this methodology was demonstrated by a gram-scale reaction. Article pubs.acs.org/joc

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Access to β‐Ketonitriles through Nickel‐Catalyzed Carbonylative Coupling of α‐Bromonitriles with Alkylzinc Reagents

Cited by 46 publications

References 40 publications

Mechanistic Investigation of the Nickel-Catalyzed Carbonylation of Alcohols

Mechanistic Investigation of the Nickel-Catalyzed Carbonylation of Alcohols

Nickel-Catalyzed Deaminative Sonogashira Coupling of Alkylpyridinium Salts Enabled by a New NN2 Pincer Ligand

Dimethylamination of Primary Alcohols Using a Homogeneous Iridium Catalyst: A Synthetic Method for N,N-Dimethylamine Derivatives

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