Activation of C–O and C–N Bonds Using Non-Precious-Metal Catalysis

Boit, Timothy B.; Bulger, Ana S.; Dander, Jacob E.; Garg, Neil K.

doi:10.1021/acscatal.0c03334

Cited by 132 publications

(76 citation statements)

References 279 publications

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“…[3] Forinstance,cleavage of CÀObonds can enable the use of abundant phenol derivatives to synthesize diverse C(aryl) linkages in catalytic arylation, alkylation, and amination reactions. [4] Similar progress has been made in the use of carboxylic acid derivatives as cross-coupling electrophiles. [5] When the carbonyl group is retained in these reactions, C(acyl) linkages can be directly obtained, providing avaluable alternative to traditional acyl substitution reactions.…”

Section: Introductionmentioning

confidence: 79%

Direct Synthesis of Ketones from Methyl Esters by Nickel‐Catalyzed Suzuki–Miyaura Coupling

et al. 2021

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The direct conversion of alkyle sters to ketones has been hindered by the sluggish reactivity of the starting materials and the susceptibility of the product towards subsequent nucleophilic attack. We have nowa chieved ac ross-coupling approach to this transformation using nickel, ab ulkyNheterocyclic carbene ligand, and alkylo rganoboron coupling partners.6 5a lkylk etones bearing diverse functional groups and heterocyclic scaffolds have been synthesized with this method. Catalyst-controlled chemoselectivity is observed for C(acyl)ÀOb ond activation of multi-functional substrates bearing other bonds prone to cleavage by Ni, including aryl ether,aryl fluoride,and N-Ph amide functional groups.Density functional theory calculations providemechanistic support for aNi 0 /Ni II catalytic cycle and demonstrate howstabilizing noncovalent interactions between the bulky catalyst and substrate are critical for the reactionssuccess.

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Section: Introductionmentioning

confidence: 79%

Direct Synthesis of Ketones from Methyl Esters by Nickel‐Catalyzed Suzuki–Miyaura Coupling

et al. 2021

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“…6,15,16,24,30 Seminal work on Ni-catalyzed cross-coupling with O-based electrophiles by Snieckus and co-workers (using Grignard reagents) 31 and later by the Garg 32 and Shi 33,34 groups (using boronic acids or zinc reagents) led to an explosion of research on Ni-based systems. 1,15,16,[22][23][24][25]35 Scheme 1 Metal-catalyzed cross-coupling with carboxylate-based electrophiles: opportunities and challenges A second significant challenge specific to the use of carboxylate-based electrophiles is achieving chemoselectivity. Whereas the C-O bond that requires activation is strong, C(acyl)-O bonds are significantly weaker (~80 kcal/mol), and there are many kinetically accessible pathways for acyl substitution (Scheme 1).…”

Section: A Mechanistic Challenge: Activating Strong C-o Bondsmentioning

confidence: 99%

C–O Bond Activation as a Strategy in Palladium-Catalyzed Cross-Coupling

Becica¹,

Leitch²

2020

Synlett

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The activation of strong C–O bonds in cross-coupling catalysis can open up new oxygenate-based feedstocks and building blocks for complex-molecule synthesis. Although Ni catalysis has been the major focus for cross-coupling of carboxylate-based electrophiles, we recently demonstrated that palladium catalyzes not only difficult C–O oxidative additions but also Suzuki-type cross-couplings of alkenyl carboxylates under mild conditions. We propose that, depending on the reaction conditions, either a typical Pd(0)/(II) mechanism or a redox-neutral Pd(II)-only mechanism can operate. In the latter pathway, C–C bond formation occurs through carbopalladation of the alkene, and C–O cleavage by β-carboxyl elimination.1 Introduction2 A Mechanistic Challenge: Activating Strong C–O Bonds3 Exploiting Vinylogy for C–Cl and C–O Oxidative Additions4 An Alternative Mechanism for Efficient Cross-Coupling Catalysis5 Conclusions and Outlook

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“…Since the first report in 2015, 39 rapid and profound progress has been made on the selective C–N bond cleavage of activated amides via a transition-metal-catalyzed system. Szostak, 40–57 Garg, 58–68 Zou, 69–71 Yamaguchi, 72–76 Huang, 77–83 Shi, 84–86 and Rueping 87–89 have made great contributions to the study of amide transformation. Our group 90–105 has also conducted excellent research in this field.…”

Section: Introductionmentioning

confidence: 99%