Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride

Samblanet, Danielle C.; Schmidt, Joseph A. R.

doi:10.1016/j.jorganchem.2012.08.027

Cited by 12 publications

(3 citation statements)

References 81 publications

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“…Following the general procedure from IPr·HCl (82.1 mg, 0.19 mmol) and [Pd(ƞ 3 -cin)(μ-Cl)] 2 (35.3 mg, 0.09 mmol), the product was obtained as a yellow powder in 99% yield (117. mg). 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) = δ 9.19 (s, 1H, C NCHN ), 8.32 (d, J = 1.6 Hz, 2H, CH Imid ), 7.54 (t, J = 8.1 Hz, 2H, CH Ar ), 7.45 (dd, J = 6.1 Hz, 2H, CH Ar(cin) ), 7.33 (d, J = 7.9 Hz, 4H, CH Ar ), 7.21 (m, 3H, CH Ar(cin) ), 5.69-5.62 (m, 1H, CH (cin) ), 4.46 (m, 1H, CH 2(cin) ), 3.86 (d, J = 6.6 Hz, 1H, CH 2(cin) ), 2.90 (d, J = 11.9 Hz, 1H, CH (cin) ), 2.48-2.41 (m, 4H, CH (IPr) ), 1.27 (d, J = 6.8 Hz, 12H, CH 3(IPr) ), 1.19 (d, J = 6.7 Hz, 12H, CH 3(IPr) ). 13 C { 1 H} NMR (400 MHz, CDCl 3 ): δ (ppm) = δ 145.1 (C Ar ), 136.9 (CH NCN ), 132.1 (CH Ar ), 129.9 (C Ar ), 128.7 (CH cin ), 127.9 (CH cin ), 127.7 (CH imid ), 124.7 (CH), 105.2 (CH cin ), 81.8 (CH cin ), 58.4 (CH 2(cin) ), 29.0 (CH (IPr) ), 24.7 (CH 3(IPr) ), 23.9 (CH 3(IPr) ).…”

Section: Synthesis Of [Ipr·h][pd(ƞ 3 -Cin)cl 2 ]mentioning

confidence: 99%

“…Following the general procedure from IPent·HCl (62.2 mg, 0.12 mmol) and [Pd(ƞ 3 -cin)(μ-Cl)] 2 (30. mg, 0.06 mmol), the product was obtained as a yellow powder in 99% (92 mg). 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) = δ 8.43 (d, J = 1.6 Hz, 2H, CH Imid ), 8.37 (br. s, 1H, C NCHN ), 7.60 (t, J = 7.9 Hz, 2H, CH Ar ), 7.50 (d, J = 7.5 Hz, 2H, CH Ar(cin) ), 7.27 (m, 7H, CH Ar ), 5.75 (br.…”

Section: Synthesis Of [Ipent·h][pd(ƞ 3 -Cin)cl 2 ]mentioning

confidence: 99%

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Palladate Precatalysts for the Formation of C–N and C–C Bonds

et al. 2019

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A series of imidazolium-based palladate precatalysts has been synthesized and the catalytic activity of these air- and moisture-stable complexes evaluated as a function of the nature of the imidazolium counterion. These precatalysts can be converted under catalytic conditions to Pd-NHC species capable of enabling the Buchwald–Hartwig aryl amination and the α-arylation of ketones. Both reactions can be carried out efficiently under very mild operating conditions. The effectiveness of the protocol was tested on functionality-laden substrates.

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Section: Synthesis Of [Ipr·h][pd(ƞ 3 -Cin)cl 2 ]mentioning

confidence: 99%

Section: Synthesis Of [Ipent·h][pd(ƞ 3 -Cin)cl 2 ]mentioning

confidence: 99%

Palladate Precatalysts for the Formation of C–N and C–C Bonds

et al. 2019

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“…In the conversion of 4 to 6 , the carboxylate served as a traceless activating group for such displacement. Alternatively, one might have considered palladium catalyzed amination of 3-bromo-5-fluoropyridine to 6 , but the traceless activation reaction is simple to run and does not incur the expense and purification issues associated with transition metal catalysis. Displacement of the 3-position fluorine with the morpholine at rt afforded carboxylic acid 5 , which upon heating underwent decarboxylation to afford 6 .…”

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confidence: 99%

Synthesis of a Tetrahydronaphthyridine Spiropyrimidinetrione DNA Gyrase Inhibiting Antibacterial Agent - Differential Substitution at all Five Carbon Atoms of Pyridine.

et al. 2014

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The synthesis of (-)-1, a potent antibacterial agent, was achieved stereoselectively in nine steps from readily available starting materials. Directed metalations were developed to assemble a pentasubstituted pyridine with appropriately positioned aldehyde and dimethylmorpholine substituents for a key tertiary amino effect reaction (T-reaction) that led to the spirocylic architecture. Ultimately, (-)-1 was isolated as the thermodynamically most favored stereoisomer.

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Design of New Ligands for the Palladium‐Catalyzed Arylation of α‐Branched Secondary Amines

et al. 2015

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In Pd-catalyzed C-N cross-coupling reactions, α-branched secondary amines are difficult coupling partners and the desired products are often produced in low yields. To provide a robust method for accessing N-aryl α-branched tertiary amines, new catalysts have been designed to suppress undesired side reactions often encountered when these amine nucleophiles are used. These advances enabled the arylation of a wide array of sterically encumbered amines, highlighting the importance of rational ligand design in facilitating challenging Pd-catalyzed cross-coupling reactions.Keywords C-N cross-coupling; amination; palladium; ligand design; synthetic methods Tertiary, N-aryl α-branched amines are frequently found as structural components of pharmaceutically relevant compounds and biologically active natural products (Figure 1). [1] Although Pd-catalyzed carbon-nitrogen (C-N) cross-coupling would provide an efficient means of accessing this valuable class of compounds, the use of α-branched secondary amine nucleophiles has seen only limited success and in many instances low yields of the desired product are obtained. [2] Other methods for preparing tertiary N-aryl α-branched amines rely on the addition of an amine to an aryne [3] or nucleophilic aromatic substitution. [4] While effective, these methods typically have a narrow substrate scope or result in a mixture of regioisomeric products. [3] Copper-catalyzed electrophilic amination has also been utilized, [5] with a recent report by Lalic demonstrating its effectiveness for the arylation of sterically hindered secondary O-benzoyl hydroxylamine electrophiles. [5b] Despite these advances, there remains no general method for the direct arylation of α-branched secondary amines. Therefore, we sought to develop a catalyst system capable of cross-coupling sterically encumbered secondary amines.Correspondence to: Stephen L. Buchwald, sbuchwal@mit.edu. Supporting information for this article is given via a link at the end of the document. HHS Public Access Author Manuscript Author ManuscriptAuthor Manuscript Author ManuscriptThe development of a highly effective catalyst system for the arylation of α-branched secondary amines must address the specific challenges presented by these coupling partners. Their poor nucleophilicity as a consequence steric hindrance can lead to slower rates of amine transmetalation, resulting in the competitive reaction of the alkoxide base and formation of the corresponding aryl tert-butyl ether (ArOtBu) (V, Figure 2). Additionally, β-hydride elimination may occur from the intermediate Pd(II)-amido complex [6,7] (IV, Figure 2) leading to the formation of the reduced arene (VI, Figure 2). In this regard, the supporting ligand for the palladium catalyst must be carefully designed in order to facilitate the preferential formation of the desired aryl amine while suppressing side reactions.We began our investigation by examining the effect of the supporting ligands on the efficiency of the catalyst system for the reaction shown in Tabl...

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Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride

Cited by 12 publications

References 81 publications

Palladate Precatalysts for the Formation of C–N and C–C Bonds

Palladate Precatalysts for the Formation of C–N and C–C Bonds

Synthesis of a Tetrahydronaphthyridine Spiropyrimidinetrione DNA Gyrase Inhibiting Antibacterial Agent - Differential Substitution at all Five Carbon Atoms of Pyridine.

Design of New Ligands for the Palladium‐Catalyzed Arylation of α‐Branched Secondary Amines

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