Nickel-Catalyzed Functionalization Reactions Involving C–H Bond Activation via an Amidate-Promoted Strategy and Its Extension to the Activation of C–F, C–O, C–S, and C–CN Bonds

Chatani, Naoto

doi:10.1021/acs.accounts.3c00493

Cited by 9 publications

(7 citation statements)

References 76 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Besides uoro-(28), bromo-(18), and iodo-substituents (27), benzamides bearing acetamido motif (33) were found to be compatible. In addition, the electrocatalytic C-H activation on thiophene enabled the enantioselective synthesis of the desired carboamination products (35,36).…”

Section: Resultsmentioning

confidence: 99%

“…In this context, the cost-effective 33 and less-toxic 34 base metal nickel as catalyst is particularly attractive [35][36][37][38][39] , which, due to its exibility in adopting various oxidation states, displays unique reactivity patterns for homogeneous catalysis 40,41 . However, the direct activation of inert C-H bonds under nickel catalysis often requires harsh reaction conditions, rendering the development of enantioselective methodologies very challenging 35,36 . The enantioselective catalyses described are limited to highly sensitive, low-valent nickel(0) precatalysts using chiral NHC 42 or HASPO 43 (pre)ligands and commonly rely on pyrophoric organoaluminium reagents 44,45 .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Nickel-electrocatalyzed enantioselective C–H activations for chemo-divergence

Ackermann,

von Münchow,

Pandit

et al. 2024

Preprint

View full text Add to dashboard Cite

Enantioselective electrocatalysis bears unique potential for the sustainable assembly of enantiomerically enriched molecules1–7. This approach allows electro-oxidative C–H activation to be performed paired to the hydrogen evolution reaction8,9. While recent progress featured scarce transition metals with limited availability10–17, we, herein, reveal that the Earth-abundant 3d transition-metal nickel is characterized by unique performance, while having high natural abundance18 and reduced toxicity19. Thereby, electrocatalytic C–H activation enabled enantioselective desymmetrizations with bicyclic alkenes, leading to three-dimensional molecular building blocks with multiple stereogenic elements20. Here, ligand optimization was guided by smart feature analysis for enantioselectivity enhancement. The detailed mechanistic investigation by experimental studies with organometallic intermediates in conjunction with computational studies identified key features of the ligand design including non-covalent interactions21,22 to guarantee full selectivity control.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nickel-electrocatalyzed enantioselective C–H activations for chemo-divergence

Ackermann,

von Münchow,

Pandit

et al. 2024

Preprint

View full text Add to dashboard Cite

show abstract

“…Enantioselective transition metal-catalyzed C–H activation represents one of the most economical and convenient routes to access chiral molecules relevant in the pharmaceutical industry, agrochemistry, fragrances, and material science. , Despite indisputable progress, enantioselective C–H functionalization continues to be dominated by precious, toxic 4d and 5d transition metals, , while more sustainable 3d metal-catalyzed transformations remain extremely challenging. , In recent decades, nickel has been widely used in C–H functionalization owing to its cost-effectiveness, low toxicity, and versatility. , However, nickel(II)-catalyzed electrophilic C–H activations typically require strong bidentate directing groups, which prevent the coordination of sterically hindered chiral ligands to the metal center. , In sharp contrast, by incorporating either a secondary phosphine oxide (SPO)-ligated Ni–Al bimetallic − catalytic system , or a Ni/N-heterocyclic carbene (NHC) , catalytic system, nickel(0)-catalyzed enantioselective C–H functionalization could be achieved without exogenous directing groups . Recently, significant advances have been made in nickel(0)-catalyzed enantioselective intramolecular cyclization reactions by Cramer, − Ye, , Ackermann, and Shi , (Figure a), while the corresponding enantioselective intermolecular transformations remain underdeveloped. − In 2022, the Shi group reported an intermolecular enantio- and regioselective nickel-catalyzed para -C–H alkylation of pyridines with styrenes enabled by an ANIPE-type NHC ligand (Figure b).…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Atroposelective C–H Alkylation Enabled by Bimetallic Catalysis with Air-Stable Heteroatom-Substituted Secondary Phosphine Oxide Preligands

Zhang,

Simon,

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The catalytic asymmetric construction of axially chiral C−N atropisomers remains a formidable challenge due to their low rotational barriers and is largely reliant on toxic, costintensive, and precious metal catalysts. In sharp contrast, we herein describe the first nickel-catalyzed atroposelective C−H alkylation for the construction of C−N axially chiral compounds with the aid of a chiral heteroatom-substituted secondary phosphine oxide (HASPO)-ligated Ni−Al bimetallic catalyst. A wide range of alkenes, including terminal and internal alkenes, were well compatible with the reaction, providing a variety of benzimidazole derivatives in high yields and enantioselectivities (up to 97:3 e.r.). The key to success was the identification of novel HASPOs as highly effective chiral preligands. Mechanistic studies revealed the catalyst mode of action, and in-depth data science analysis elucidated the key features of the responsible chiral preligands in controlling the enantioselectivity.

show abstract

“…This is because there is value in being able to use a widely available but largely underutilized monomer class in a diverse range of transformations. Under this trend, aromatic esters have gained considerable attention as a replacement for aryl halides alongside carboxylic acids and its other derivatives, phenol derivatives, diazonium salts, nitroarenes, and other arene scaffolds …”

Section: Introductionmentioning

confidence: 99%

Divergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling

Kubo,

Yamaguchi

2024

Acc. Chem. Res.

View full text Add to dashboard Cite

Conspectus Aromatic esters are cost-effective, versatile, and commonly used scaffolds that are readily synthesized or encountered as synthetic intermediates. While most conventional reactions involving these esters are nucleophilic acyl substitutions or 1,2-nucleophilic additionswhere a nucleophile attacks the carbonyl group, decarbonylative transformations offer an alternative pathway by using the carbonyl group as a leaving group. This transition-metal-catalyzed process typically begins with oxidative addition of the C(acyl)–O bond to the metal. Subsequently, the reaction involves the migration of CO to the metal center, the reaction with a nucleophile, and reductive elimination to yield the final product. Pioneering work by Yamamoto on nickel complexes and the development of decarbonylative reactions (such as Mizoroki–Heck-type olefination) using aromatic carboxylic anhydrides catalyzed by palladium were conducted by de Vries and Stephan. Furthermore, reports have surfaced of decarbonylative hydrogenation of pyridyl methyl esters by Murai using ruthenium catalysts as well as Mizoroki–Heck-type reactions of nitro phenyl esters by Gooßen under palladium catalysis. Our group has been at the forefront of developing decarbonylative C–H arylations of phenyl esters with 1,3-azoles and aryl boronic acids using nickel catalysts. The key to this reaction is the use of phenyl esters, which are easy to synthesize, stabilize, and handle, allowing oxidative addition of the C(acyl)–O bond; nickel, which facilitates oxidative addition of the C(acyl)–O bond; and suitable bidentate phosphine ligands that can stabilize the intermediate. By modification of the nucleophiles, esters have been effectively utilized as electrophiles in cross-coupling reactions, encouraging the development of these nucleophiles among researchers. This Account summarizes our advancements in nucleophile development for decarbonylative coupling reactions, particularly highlighting the utilization of aromatic esters in diverse reactions such as alkenylation, intramolecular etherification, α-arylation of ketones, C–H arylation, methylation, and intramolecular C–H arylation for dibenzofuran synthesis, along with cyanation and reductive coupling. We also delve into reaction types that are distinct from typical decarbonylative reactions, including ester dance reactions, aromatic ring exchanges, and deoxygenative transformations, by focusing on the oxidative addition of the C(acyl)–O bond of the aromatic esters to the metal complex. For example, the ester dance reaction is hypothesized to undergo 1,2-translocation starting with oxidative addition to a palladium complex, leading to a sequence of ortho-deprotonation/decarbonylation, followed by protonation, carbonylation, and reductive elimination. The aromatic exchange reaction likely involves oxidative addition of complexes of different aryl electrophiles with a nickel complex. In deoxygenative coupling, an oxidative addition complex with palladium engages with a nucleophile, forming an acyl intermediate that ...

show abstract

Nickel-Catalyzed Functionalization Reactions Involving C–H Bond Activation via an Amidate-Promoted Strategy and Its Extension to the Activation of C–F, C–O, C–S, and C–CN Bonds

Cited by 9 publications

References 76 publications

Nickel-electrocatalyzed enantioselective C–H activations for chemo-divergence

Nickel-electrocatalyzed enantioselective C–H activations for chemo-divergence

Nickel-Catalyzed Atroposelective C–H Alkylation Enabled by Bimetallic Catalysis with Air-Stable Heteroatom-Substituted Secondary Phosphine Oxide Preligands

Divergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling

Contact Info

Product

Resources

About