The Preparation of Some Monosubstituted Derivatives of Pyrrole by the Mannich Reaction

Herz, Werner; Dittmer, Karl; Cristol, Stanley J.

doi:10.1021/ja01199a038

Cited by 83 publications

(47 citation statements)

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“…The reaction of LiAlH 4 with [C 4 H 4 N(CH 2 NMe 2 )-2] [11] in diethyl ether at 0 8C generated AlH[C 4 H 3 N(CH 2 NMe 2 )-2] 2 (1) in 80 % yield (Scheme 1). Compound 1 was the only product isolated, even when the ratio of LiAlH 4 /[C 4 H 4 N(CH 2 NMe 2 )-2] was varied from 1.0 to 2.0.…”

Section: Resultsmentioning

confidence: 99%

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Insertion, Reduction, and Carbon–Carbon Coupling Induced by Monomeric Aluminum Hydride Compounds Bearing Substituted Pyrrolyl Ligands

Lin¹,

Tsai²,

Chen³

et al. 2006

Chemistry A European J

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A monomeric aluminum hydride complex bearing substituted pyrrolyl ligands, AlH[C(4)H(3)N(CH(2)NMe(2))-2](2) (1), was synthesized and structurally characterized. To further confirm the presence of Al--H bonds, the compound AlD[C(4)H(3)N(CH(2)NMe(2))-2](2) ([D]1) was synthesized by reacting LiAlD(4) with [C(4)H(4)N(CH(2)NMe(2))-2]. Compound 1 and [D]1 react with phenyl isothiocyanate yielding Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCHNPh] (2) and Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCDNPh] ([D]2) by insertion. The reactions of 1 with 9-fluorenone and benzophenone generated the unusual aluminum alkoxide complexes 3 and 4, respectively, through intramolecular proton abstraction and C-C coupling. A mechanistic study shows that 9-fluorenone coordinates to [D]1 and releases one equivalent of HD followed by C-C coupling and hydride transfer to yield the final product. Reduction of benzil with 1 affords aluminum enediolate complex 5 in moderate yield. Mechanistic studies also showed that the benzil was inserted into the aluminum hydride bond of [D]1 through hydroalumination followed by proton transfer to generate the final product [D]5. All new complexes have been characterized by (1)H and (13)C NMR spectroscopy and X-ray crystallography.

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Section: Resultsmentioning

confidence: 99%

“…[C 4 H 3 NH(CH 2 NMe 2 )-2] was prepared according to a previously reported procedure. [11] LiAlH 4 , 9-flurorenone, and phenyl isothiocyanate (Aldrich) were used as received. .…”

Section: Methodsmentioning

confidence: 99%

Insertion, Reduction, and Carbon–Carbon Coupling Induced by Monomeric Aluminum Hydride Compounds Bearing Substituted Pyrrolyl Ligands

Lin¹,

Tsai²,

Chen³

et al. 2006

Chemistry A European J

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“…There are no noticeable differences toward the ring-opening polymerization relating to metals (Zr or Hf) or bulkiness of the substituted aryloxides and pyrrolyl ligands of compounds 3-8. [40,41] C 4 H 3 NH-(CH 2 NMe 2 )-2, [42,43] and M(NEt 2 ) 4 (M = Zr, Hf) [44] were prepared according to previously reported procedures.…”

Section: Polymerization Of ε-Caprolactonementioning

confidence: 99%

Synthesis and Characterization of Zirconium and Hafnium Aryloxide Compounds and Their Reactivity Towards Lactide and ϵ‐Caprolactone Polymerization

et al. 2006

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Reactions of 2 equiv. pyrrole with [C4H3N(CH2NMe2)‐2]2M(NEt2)2 in toluene generated tetra‐pyrrolyl metal compounds [C4H3N(CH2NMe2)‐2]2M(C4H4N)2 (3, M = Zr; 4, M = Hf) in moderate yields. Similarly, treatment of metal amides [C4H3N(CH2NMe2)‐2]2M(NEt2)2 with 2,6‐dimethylphenol or 2,6‐diisopropylphenol in heptane resulted in the elimination of diethylamine along with the formation of the corresponding metal alkoxides [C4H3N(CH2NMe2)‐2]2M(OR)2 (5, M = Zr, R = C6H3‐2,6‐Me2; 6, M = Hf, R = C6H3‐2,6‐Me2; 7, M = Zr, R = C6H3‐2,6‐iPr2; 8, M = Hf, R = C6H3‐2,6‐iPr2) in moderate yields. All the new compounds were characterized by 1H and 13C NMR spectroscopy and the structures of 3, 4, 6, 7, and 8 have also been determined by X‐ray crystallographic studies. The aryloxides and the substituted pyrrolyl ligands in both compounds 5 and 6 show fluxionality as observed by 1H NMR signals. A kinetic study on the ring‐opening polymerization of lactide exhibits a first‐order reaction of lactide monomer with compound 8. The catalytic properties of all the metal complexes have been studied for the ring‐opening polymerization of ϵ‐caprolactone. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…Likewise, pyrrole (1) may be converted in high yield into 2-(dimethylaminomethyl)pyrrole 232 via the Mannich reaction (Scheme 4.62) [344]. It has also been found that pyrrole adds upon heating (neat) to 1-pyrroline 233, leading to 2-(pyrrolidin-2-yl)pyrrole (234) [345].…”

Section: Nitrationmentioning

confidence: 99%

Five‐Membered Heterocycles: Pyrrole and Related Systems

Bergman

Janosik

2011

Modern Heterocyclic Chemistry

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The Preparation of Some Monosubstituted Derivatives of Pyrrole by the Mannich Reaction

Cited by 83 publications

References 0 publications

Insertion, Reduction, and Carbon–Carbon Coupling Induced by Monomeric Aluminum Hydride Compounds Bearing Substituted Pyrrolyl Ligands

Insertion, Reduction, and Carbon–Carbon Coupling Induced by Monomeric Aluminum Hydride Compounds Bearing Substituted Pyrrolyl Ligands

Synthesis and Characterization of Zirconium and Hafnium Aryloxide Compounds and Their Reactivity Towards Lactide and ϵ‐Caprolactone Polymerization

Five‐Membered Heterocycles: Pyrrole and Related Systems

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