Direct Access to Isotopically Labeled Aliphatic Ketones Mediated by Nickel(I) Activation

Donslund, Aske S.; Pedersen, Simon S.; Gaardbo, Cecilie; Neumann, Karoline T.; Kingston, Lee P.; Elmore, Charles S.; Skrydstrup, Troels

doi:10.1002/ange.201916391

Cited by 9 publications

(1 citation statement)

References 47 publications

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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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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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Regioselective Hydroalkylation of Vinylarenes by Cooperative Cu and Ni Catalysis

2021

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Disclosed here is a dual copper and nickel catalytic system with a silyl hydride source for promoting the linear selective hydroalkylation of vinylarenes. This carbon–carbon bond‐forming protocol is applied to couple a variety of functionalized vinylarenes with alkyl halides applying a nickel(II) NNN pincer complex in the presence of an NHC‐ligated copper catalyst. This combination allows for a 1 mol % loading of the nickel catalyst leading to turnover numbers of up to 72. Over 40 examples are presented, including applications for pharmaceutical diversification. Labeling experiments demonstrated the regioselectivity of the reaction and revealed that the copper catalyst plays a crucial role in enhancing the rate for formation of the reactive linear alkyl nickel complex. Overall, the presented work provides a complimentary approach for hydroalkylation reactions, whilst providing a preliminary mechanistic understanding of the cooperativity between the copper and nickel complexes.

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Nickel‐Catalyzed Asymmetric Hydroaryloxy‐ and Hydroalkoxycarbonylation of Cyclopropenes

Cai

et al. 2022

Angewandte Chemie

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The asymmetric Reppe carbonylation reactions provide a straightforward access to α-chiral carbonyl compounds. The reported paradigms predominantly adopted precious palladium as the catalyst. Here we report a nickel-catalyzed asymmetric carbonylation of cyclopropenes with phenyl formate and CO/ROH, respectively. This asymmetrical synthetic protocol features high atom economy, good functional group tolerance, which rapidly constructs polysubstituted cyclopropanecarboxylic derivatives with excellent diastereoand enantioselectivity. The synthetic utility is demonstrated by facile conversion of the chiral products into bioactive molecules such as (À )-Tranylcypromine and (À )-Lemborexant.

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Direct Access to Isotopically Labeled Aliphatic Ketones Mediated by Nickel(I) Activation

Cited by 9 publications

References 47 publications

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

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

Regioselective Hydroalkylation of Vinylarenes by Cooperative Cu and Ni Catalysis

Nickel‐Catalyzed Asymmetric Hydroaryloxy‐ and Hydroalkoxycarbonylation of Cyclopropenes

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