Umsetzung von Nitroaromaten mit Grignard‐Verbindungen, III

Severin, Theodor; Adam, Manfred

doi:10.1002/cber.19640970126

Cited by 20 publications

(3 citation statements)

References 8 publications

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“…This reductive nitro-Mannich reaction formed β,δ-dinitroamines 46 with piperidine and bicylic products 47 with methylamine, which were formed in good yields for a number of substituted dinitrobenzenes. The same group also demonstrated that similar reactions could be performed using Grignard reagents in place of NaBH 4 . This methodology has since been extended to a variety of other m -dinitroaromatic, dinitrobicycloaromatic, and dinitroheteroaromatic rings. − …”

Section: Early Developmentsmentioning

confidence: 94%

Nitro-Mannich Reaction

2013

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Section: Early Developmentsmentioning

confidence: 94%

Nitro-Mannich Reaction

2013

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“…Thus, addition of formalin and methylamine to the Meisenheimer complexes obtained in the reaction of 447a,b with an excess of Grignard reagents followed by treatment with acetic acid produced the 3-azabicyclo[3.3.1]non-6-enes 505 in yields from 12 to 35% (Scheme 76). 270 For 5-methoxy-1,3-dinitrobenzene 447j the expected bicyclic compound 506 was obtained in 37% yield. However, the reaction mixture had to be refluxed for 5 h; otherwise, unreacted 447j was recovered.…”

Section: Reactions With Nonstabilized Carbanionsmentioning

confidence: 98%

“…Similar to the borohydride reduction of nitroarenes, the dialkylated σ-diadducts were also trapped through Mannich reactions. Thus, addition of formalin and methylamine to the Meisenheimer complexes obtained in the reaction of 447a , b with an excess of Grignard reagents followed by treatment with acetic acid produced the 3-azabicyclo[3.3.1]non-6-enes 505 in yields from 12 to 35% (Scheme ) …”

Section: 12 Reactions With Nonstabilized Carbanionsmentioning

confidence: 99%

Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

et al. 2007

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Institute fu ¨r Kohlenforschung (Mu ¨lheim a.d. Ruhr) with R. Benn investigating 187 Os NMR. In November 1989 he became Profesor Titular at the University of Oviedo, where he started his own research. He moved to the University of Almerı ´a (1996), where he is Professor of Organic Chemistry. His current research activities range from the application of phosphorus-stabilized carbanions in organic and organometallic chemistry to mechanistic studies of reactions involving organometallic species through multinuclear magnetic resonance. G. Ruiz Go ´mez was born in Madrid, Spain. She studied chemistry at the University of Almerı ´a and completed her first degree (Licenciatura) in July 2000. She was awarded a Ph.D. in 2006 for work on dearomatizing reactions of phosphinamides and phosphonamides under the direction of Professor Lo ´pez Ortiz. She is currently a postdoctoral fellow in Professor Lo ´pez-Ortiz's group with interest in the synthesis of non-natural peptides and peptide analogues.

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General Preparation of Functionalized o ‐Nitroarylmagnesium Halides through an Iodine–Magnesium Exchange

Sapountzis

Knöchel

2002

Angewandte Chemie

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Dedicated to Professor Lutz F. Tietze on the occasion of his 60th birthdayThe preparation of functionalized organometallic compounds is an important research field since it allows the formation of new C À C bonds between polyfunctional nucleophiles and electrophiles, leading to multifunctional products. [1] Although organozinc compounds have proved to be very useful, the recent use of the I ± Mg exchange allows the straightforward synthesis of various highly functionalized aryl-, [2] heteroaryl-, [3] and alkenylmagnesium [4] reagents. Nitro groups are present in many important aromatic compounds, [5] but have been regarded as being incompatible with organometallic species. [6] Only scarce examples of nitro-substituted aryl organometallic compounds have been reported. [7] Herein we wish to report that the I ± Mg exchange allows an efficient preparation of polyfunctional arylmagnesium reagents that bear a nitro group ortho to the iodine atom. Furthermore, we will show that this new class of organomagnesium compounds is compatible with several transition metal catalyzed crosscoupling reactions. In a preliminary experiment, we treated 2-iodonitrobenzene (1 a) with phenylmagnesium chloride (1.1 equiv) in THF at À 40 8C. Within 5 min, a complete I ± Mg exchange was observed, as indicated by GC analysis of reaction aliquots. The resulting nitro-substituted Grignard reagent (2 a) reacted with benzaldehyde (1.2 equiv) within 0.5 h at À 40 8C to give the expected benzhydryl alcohol (3 a) in 87 % yield (Scheme 1 and Table 1, entry 1). NO 2 I FG FG NO 2 MgCl FG NO 2 E PhMgCl -40 °C 5 min E + 2a -f 3 a -m: 64 -94 % 1a: FG = H; b: FG = 5-CN; c: FG = 4-OMe; d: FG = 4-CO 2 Et; e: FG = 4-NO 2 ; f: FG = 4-I Scheme 1. Preparation of o-nitro substituted arylmagnesium reagents.

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Umsetzung von Nitroaromaten mit Grignard‐Verbindungen, III

Cited by 20 publications

References 8 publications

Nitro-Mannich Reaction

Nitro-Mannich Reaction

Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

General Preparation of Functionalized o ‐Nitroarylmagnesium Halides through an Iodine–Magnesium Exchange

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Umsetzung von Nitroaromaten mit Grignard‐Verbindungen, III

Cited by 20 publications

References 8 publications

Nitro-Mannich Reaction

Nitro-Mannich Reaction

Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

General Preparation of Functionalized o ‐Nitroarylmagnesium Halides through an Iodine–Magnesium Exchange

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Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis