Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp<sup>2</sup> and sp<sup>3</sup> C–H Bonds

Nadres, Enrico T.; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs

doi:10.1021/jo4013628

Cited by 229 publications

(113 citation statements)

References 94 publications

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“…In the event that two chemically equivalent positions exist, bis-arylation is observed. This is in agreement with similar Pd-catalyzed reactions where bis-arylation is occasionally observed [93]. Alkyl halides can also serve as electrophiles for these reactions, although a bidentate phosphine ligand is required [95].…”

Section: Nickel Catalysissupporting

confidence: 88%

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High-Valent Co(III)- and Ni(II)-Catalyzed C–H Activation

Hyster

2014

Catal Lett

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The past two decades have witnessed explosive growth in the field of catalytic C-H activation. While this reactivity is typically associated with second-and thirdrow transition metals, first-row transition metals are also capable of catalyzing these reactions. C-H activation reactions can be further divided into ones where the C-H activation occurs with a low-valent metal and those where the activation occurs with a high-valent metal. This review will summarize advances in the area of high-valent Co(III)-and Ni(II)-catalyzed C-H activation with particular emphasis paid to how these catalysts compare their secondand third-row congeners.

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Section: Nickel Catalysissupporting

confidence: 88%

“…These mechanisms closely resemble the proposed mechanism for the analogous reactivity with Pd. In these cases, Daugulis proposes a Pd(II)-Pd(IV) redox cycle to be operative [59,60,93,94].…”

Section: Nickel Catalysismentioning

confidence: 99%

High-Valent Co(III)- and Ni(II)-Catalyzed C–H Activation

Hyster

2014

Catal Lett

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“…20 Since free benzylamines can be arylated by ArI under palladium catalysis, 13c the use of the picolinic acid directing group in these substrates was not extensively investigated. However, Ag(I) oxidizes 1-naphthylamine.…”

Section: Design Of Bidentate Monoanionic Auxiliaries and Palladiumentioning

confidence: 99%

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

2015

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CONSPECTUS In recent years, carbon–hydrogen bond functionalization has evolved from an organometallic curiosity to mainstream applications in the synthesis of complex natural products and drugs. The use of C–H bonds as a transformable functional group is advantageous because these bonds are the most abundant functionality in organic molecules. One-step conversion of these bonds to the desired functionality shortens synthetic pathways, saving reagents, solvents, and labor. Less chemical waste is generated as well, showing that this chemistry is environmentally beneficial. This Account describes the development and use of bidentate, monoanionic auxiliaries for transition-metal-catalyzed C–H bond functionalization reactions. The chemistry was initially developed to overcome the limitations with palladium-catalyzed C–H bond functionalization assisted by monodentate directing groups. By the use of electron-rich bidentate directing groups, functionalization of unactivated sp3 C–H bonds under palladium catalysis has been developed. Furthermore, a number of abundant base-metal complexes catalyze functionalization of sp2 C–H bonds. At this point, aminoquinoline, picolinic acid, and related compounds are among the most used and versatile directing moieties in C–H bond functionalization chemistry. These groups facilitate catalytic functionalization of sp2 and sp3 C–H bonds by iron, cobalt, nickel, copper, ruthenium, rhodium, and palladium complexes. Exceptionally general reactivity is observed, enabling, among other transformations, direct arylation, alkylation, fluorination, sulfenylation, amination, etherification, carbonylation, and alkenylation of carbon–hydrogen bonds. The versatility of these auxilaries can be attributed to the following factors. First, they are capable of stabilizing high oxidation states of transition metals, thereby facilitating the C–H bond functionalization step. Second, the directing groups can be removed, enabling their use in synthesis and functionalization of natural products and medicinally relevant substances. While the development of these directing groups presents a significant advance, several limitations of this methodology are apparent. The use of expensive second-row transition metal catalysts is still required for efficient sp3 C–H bond functionalization. Furthermore, a disadvantage is the need to install and subsequently remove the relatively expensive directing group.

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“…6 The synthetic procedure is summarized in Scheme 1. Picolinic acid 1-naphthylamide was coupled with 3,5-dichloroiodobenzene to yield N -(8-(3,5-dichlorophenyl)-naphthalen-1-yl)picolinamide ( 4 ) in 77% yield.…”

Section: Synthesis Of Complexesmentioning

confidence: 99%

Synthesis and Properties of “Sandwich” Diimine-Coinage Metal Ethylene Complexes

2016

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Synthesis and full characterization of cationic isostructural “sandwich” diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a. The upper limit of ΔG‡, assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with ΔG298‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9, with ΔG298‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

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Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp² and sp³ C–H Bonds

Cited by 229 publications

References 94 publications

High-Valent Co(III)- and Ni(II)-Catalyzed C–H Activation

High-Valent Co(III)- and Ni(II)-Catalyzed C–H Activation

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

Synthesis and Properties of “Sandwich” Diimine-Coinage Metal Ethylene Complexes

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Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C–H Bonds

Cited by 229 publications

References 94 publications

High-Valent Co(III)- and Ni(II)-Catalyzed C–H Activation

High-Valent Co(III)- and Ni(II)-Catalyzed C–H Activation

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

Synthesis and Properties of “Sandwich” Diimine-Coinage Metal Ethylene Complexes

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Product

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Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp² and sp³ C–H Bonds