Synthesis of Biaryl Ethers by the Copper-Catalyzed Chan–Evans–Lam Etherification from Benzylic Amine Boronate Esters

Marcum, Justin S.; McGarry, Kathryn A.; Ferber, Carl J.; Clark, Timothy B.

doi:10.1021/acs.joc.6b01254

Cited by 16 publications

(13 citation statements)

References 58 publications

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“…In 2016, Clark and co-workers used the Cu-catalyzed etherification of ortho-[(dimethylamino)methyl]phenylboronic acid pinacol esters with phenols to give aryl 2-[(dimethylamino)methyl]phenyl ethers (Scheme 104). 89 This is similar to their amination work described in Section 2.1.2 (Scheme 23). 31a Various substituted arylboronate esters and phenols underwent the reaction smoothly to furnish the product in moderate to high yields.…”

Section: Scheme 103 Cu(otf) 2 /Ag 2 Co 3 -Catalyzed Coupling Of Carbosupporting

confidence: 75%

Advances in Carbon–Element Bond Construction under Chan–Lam Cross-Coupling Conditions: A Second Decade

et al. 2020

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Copper-mediated carbon–heteroatom bond-forming reactions involving a wide range of substrates have been in the spotlight for many organic chemists. This review highlights developments between 2010 and 2019 in both stoichiometric and catalytic copper-mediated reactions, and also examples of nickel-mediated reactions, under modified Chan–Lam cross-coupling conditions using various nucleophiles; examples include chemo- and regioselective N-arylations or O-arylations. The utilization of various nucleophiles as coupling partners together with reaction optimization (including the choice of copper source, ligands, base, and other additives), limitations, scope, and mechanisms are examined; these have benefitted the development of efficient and milder methods. The synthesis of medicinally valuable or pharmaceutically important nitrogen heterocycles, including isotope-labeled compounds, is also included. Chan–Lam coupling reaction can now form twelve different C–element bonds, making it one of the most diverse and mild reactions known in organic chemistry.1 Introduction2 Construction of C–N and C–O Bonds2.1 C–N Bond Formation2.1.1 Original Discovery via Stoichiometric Copper-Mediated C–N Bond Formation2.1.2 Copper-Catalyzed C–N Bond Formation2.1.3 Coupling with Azides, Sulfoximines, and Sulfonediimines as Nitrogen Nucleophiles2.1.4 Coupling with N,N-Dialkylhydroxylamines2.1.5 Enolate Coupling with sp3-Carbon Nucleophiles2.1.6 Nickel-Catalyzed Chan–Lam Coupling2.1.7 Coupling with Amino Acids2.1.8 Coupling with Alkylboron Reagents2.1.9 Coupling with Electron-Deficient Heteroarylamines2.1.10 Selective C–N Bond Formation for the Synthesis of Heterocycle-Containing Compounds2.1.11 Using Sulfonato-imino Copper(II) Complexes2.2 C–O Bond Formation2.2.1 Coupling with (Hetero)arylboron Reagents2.2.2 Coupling with Alkyl- and Alkenylboron Reagents3 C–Element (Element = S, P, C, F, Cl, Br, I, Se, Te, At) Bond Forma tion under Modified Chan–Lam Conditions4 Conclusions

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Section: Scheme 103 Cu(otf) 2 /Ag 2 Co 3 -Catalyzed Coupling Of Carbosupporting

confidence: 75%

Advances in Carbon–Element Bond Construction under Chan–Lam Cross-Coupling Conditions: A Second Decade

et al. 2020

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“…etherification of phenols under similar conditions 141. Similar to Clark, Xu subsequently demonstrated that a range of carbonyl groups could also promote ArBPin cross-coupling via Cu-coordination 159.…”

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confidence: 78%

“…75 The primary focus of this study was to address a common problem in the Chan-Lam amination when using arylboronic acid pinacol esters (BPin), which are known to be significantly less effective in Chan-Lam processes with the exception of several specific reports. [139][140][141][142] This reactivity problem was also reported to be more profound with arylamines than alkylamines. 100 Watson investigated a benchmark stoichiometric amination reaction using an arylboronic acid with exemplar aryl and alkyl amines as shown in Scheme 40a leading to the mechanistic proposal shown in Scheme 40b.…”

Section: Mechanistic Investigations In the Amination Reactionmentioning

confidence: 99%

Mechanistic Development and Recent Applications of the Chan–Lam Amination

et al. 2019

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1. INTRODUCTION 1.1 Generalities and Context 1.2 C-N Bond Formation via Cross-Coupling Reactions 1.3 C-N Bond Formation via Nucleophile-Electrophile Cross-Coupling 1.4 C-N Bond Formation via Nucleophile-Nucleophile Cross-Coupling 2. DISCUSSION 2.1 Discovery 2.2 Development of Reaction Conditions 2.3 A General Mechanistic Description of the Chan-Lam Reaction 2.4 Reactions Variables and Selection of Reaction Conditions 3. SCOPE OF THE CHAN-LAM AMINATION 3.1 Organoboron Variation 3.2 Aryl Amines (Anilines) 3.3 Heteroaryl Amines (Heterocyclic Anilines) 3.4 Alkyl Amines 3.5 Amides 3.6 NH-Heterocycles 3.7 C-N Bond Formation to non-NH-Nucleophiles 3.8 Sulfonamides and Sulfoximes 3.9 Sequential Processes 3.10 C-N Bond Formation on Nucleobases and Peptides 4. MECHANISM 4.1 Historical Context 4.2 Mechanistic Investigations in the Etherification Reaction 4.3 Mechanistic Investigations in the Amination Reaction 4.4 Mechanistic Investigations in the Amination Reaction: Ligand-based Systems 4.5 Mechanism Summary

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“…These results complement the relatively few reported cases of the use of boronic acid derivatives as partners for Chan-Evans-Lam coupling. 27,28 In contrast, the boronic acids 10a and 10b bearing a keto group were found to be unsuitable reaction partners for the synthesis of the corresponding quinazolines 11a and 11b (Scheme 2). In the case of these substrates, complex mixtures were obtained containing the O-arylation products 12a and 12b as the only identifiable byproducts.…”

Section: Syn Lettmentioning

confidence: 99%

2-Aminoquinazolines by Chan–Evans–Lam Coupling of Guanidines with (2-Formylphenyl)boronic Acids

Solomin

Seins

Jirgensons

2020

Synlett

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A new method is presented for the synthesis of 2-aminoquinazolines, which is based on a Chan–Evans–Lam coupling of (2-formylphenyl)boronic acids with guanidines. Relatively mild conditions involving the use of inexpensive CuI as a catalyst and methanol as a solvent permit the application of the method to a wide range of substrates. Nonsubstituted, N-monosubstituted, and N,N-disubstituted guanidines can be used as reactants to give the corresponding 2-aminoquinazolines in moderate yields from readily available (2-formylphenyl)boronic acids.

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Synthesis of Biaryl Ethers by the Copper-Catalyzed Chan–Evans–Lam Etherification from Benzylic Amine Boronate Esters

Cited by 16 publications

References 58 publications

Advances in Carbon–Element Bond Construction under Chan–Lam Cross-Coupling Conditions: A Second Decade

Advances in Carbon–Element Bond Construction under Chan–Lam Cross-Coupling Conditions: A Second Decade

Mechanistic Development and Recent Applications of the Chan–Lam Amination

2-Aminoquinazolines by Chan–Evans–Lam Coupling of Guanidines with (2-Formylphenyl)boronic Acids

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