An Efficient Assembly of Heterobenzazepine Ring Systems Utilizing an Intramolecular Palladium-Catalyzed Cycloamination

Margolis, Brandon J.; Swidorski, Jacob J.; Rogers, Bruce N.

doi:10.1021/jo026546g

Cited by 58 publications

(23 citation statements)

References 14 publications

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“…Diisopropylamine was dried over potassium hydroxide, dioxane was dried over calcium hydride. 31 P NMR. Abbreviations for NMR data: s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, dt = doublet of triplets, dq = doublet of quartets, tt = triplet of triplets, m = multiplet.…”

Section: Methodsmentioning

confidence: 99%

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

Fleckenstein

Plenio

2007

Chemistry A European J

173

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The lithiation/alkylation of fluorene leads to various 9-alkyl-fluorenes (alkyl=Me, Et, iPr, -Pr, -C18H25) in>95% yields, for which lithiation and reaction with R2PCl (R=Cy, iPr, tBu) generates 9-alkyl, 9-PR2-fluorenes which constitute electron-rich and bulky phosphine ligands. The in-situ-formed palladium-phosphine complexes ([Na2PdCl4], phosphonium salt, base, substrates) were tested in the Sonogashira, Suzuki, and Buchwald-Hartwig reactions of aryl chlorides and aryl bromides in organic solvents. The Sonogashira coupling of aryl chlorides at 100-120 degrees C leads to>90% yields with 1 mol% of Pd catalyst. The Suzuki coupling of aryl chlorides typically requires 0.05 mol% of Pd catalyst at 100 degrees C in dioxane for quantitative product formation. To carry out "green" cross-coupling reactions in water, 9-ethylfluorenyldicyclohexylphosphine was reacted in sulphuric acid to generate the respective 2-sulfonated phosphonium salt. The Suzuki coupling of activated aryl chlorides by using this water-soluble catalyst requires only 0.01 mol% of Pd catalyst, while a wide range of aryl chlorides can be quantitatively converted into the respective coupling products by using 0.1-0.5 mol% of catalyst in pure water at 100 degrees C. Difficult substrate combinations, such as naphthylboronic acid or 3-pyridylboronic acid and aryl chlorides are coupled at 100 degrees C by using 0.1-0.5 mol% of catalyst in pure water to obtain the respective N-heterocycles in quantitative yields. The copper-free aqueous Sonogashira coupling of aryl bromides generates the respective tolane derivatives in>95% yield.

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Section: Methodsmentioning

confidence: 99%

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

Fleckenstein

Plenio

2007

Chemistry A European J

173

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“…The scale is also larger owing to the potential scale-up work for future production. For example, Rogers (Entry 4) [116] reports the intramolecular 7-ring formation on a 20-g scale. One of the largest scale applications reported in the literature is the synthesis of CP 529,414 which was published on a 3-kg scale in two patents by Pfizer using Buchwalds ligand Dave-Phos (Entry 7).…”

Section: Applications From Industrial Groupsmentioning

confidence: 99%

Palladium‐Catalyzed CN and CO Coupling–A Practical Guide from an Industrial Vantage Point^†

2004

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The palladium-catalyzed coupling of amines with aryl halides or aryl alcohol derivatives, commonly dubbed Buchwald-Hartwig amination, has matured from a synthetic laboratory procedure to a technique that is widely used in natural product synthesis as well as in other fields of academic interest. Furthermore, due to the versatility and reliability of this reaction, researchers in industrial environments have included this methodology in their toolbox as a standard procedure for the synthesis of amine derivatives. Therefore, it is not surprising that first industrial processes up to ton-scale have been performed using this cross-coupling reaction. The authors who are involved in the application of this reaction to industrial processes on this scale give an overview of the recent developments in this field of chemistry, also including fundamental principles, with a special focus on the industrial approach and issues to be considered relevant in scaling-up this transition metal-catalyzed chemistry. This review differs from the already existing excellent academic reviews by focusing on the practical problems arising during implementing the methodology in an industrial environment as well as giving practical hints to this end.

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“…The structures of the compounds were further confirmed by 13 C NMR and DEPT135 spectroscopy for the protonated carbons. The 13 C NMR spectra provide direct information about the carbon skeleton of the molecule.…”

Section: Nmr Spectroscopymentioning

confidence: 87%

“…The 1 H NMR, 13 C NMR spectroscopy were used to further substantiate the molecular structure of the title compounds in DMSO at ambient temperature.…”

Section: Characterization By Nmr Spectramentioning

confidence: 99%

Synthesis and Characterization of New 3‐(3‐Hydroxyphenyl)‐4‐ alkyl‐3,4‐dihydrobenzo[e][1,3]oxazepine‐1,5‐dione Compounds

et al. 2011

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A series of 3-(3-hydroxyphenyl)-4-alkyl-3,4-dihydrobenzo[e][1,3]oxazepine-1,5-dione compounds with general formula C n H 2n＋1 CNO(CO) 2 C 6 H 4 (C 6 H 4 OH) in which n are even parity numbers from 2 to 18. The structure determinations on these compounds were performed by FT-IR spectroscopy which indicated that the terminal alkyl chain attached to the oxazepine ring was fully extended. Conformational analysis in DMSO at ambient temperature was carried out for the first time via high resolution 1 H NMR and 13 C NMR spectroscopy.

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An Efficient Assembly of Heterobenzazepine Ring Systems Utilizing an Intramolecular Palladium-Catalyzed Cycloamination

Cited by 58 publications

References 14 publications

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

Palladium‐Catalyzed CN and CO Coupling–A Practical Guide from an Industrial Vantage Point^†

Synthesis and Characterization of New 3‐(3‐Hydroxyphenyl)‐4‐ alkyl‐3,4‐dihydrobenzo[e][1,3]oxazepine‐1,5‐dione Compounds

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An Efficient Assembly of Heterobenzazepine Ring Systems Utilizing an Intramolecular Palladium-Catalyzed Cycloamination

Cited by 58 publications

References 14 publications

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

Palladium‐Catalyzed CN and CO Coupling–A Practical Guide from an Industrial Vantage Point†

Synthesis and Characterization of New 3‐(3‐Hydroxyphenyl)‐4‐ alkyl‐3,4‐dihydrobenzo[e][1,3]oxazepine‐1,5‐dione Compounds

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Palladium‐Catalyzed CN and CO Coupling–A Practical Guide from an Industrial Vantage Point^†