Aldehydes by Formylation of Grignard or Organolithium Reagents with <i>N</i>‐Formylpiperidine

Oláh, George A.; Arvanaghi, Massoud

doi:10.1002/anie.198108781

Cited by 78 publications

(25 citation statements)

References 8 publications

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“…N-Formyl morpholine (16), Nformylpiperidine (17), and DMF (18) are often employed as the amide component. The reaction is considered to proceed through addition of the organometallic reagent to the amide carbony1 to afford a metalated hemiaminal.…”

Section: Enamines By Reaction Of Lithiated Methyl Pyridines Withmentioning

confidence: 99%

Enamines from formamides. Synthesis of 1,2,3,4-tetrahydro-1-substituted β-carbolines

Vohra¹,

MacLean²

1994

Can. J. Chem.

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RAHUL VOHRA and DAVID B. MACLEAN. Can. J. Chem. 72, 1660Chem. 72, (1994.Pyridines and benzopyridines substituted with trimethylsilylmethyl groups, a or y to the nitrogen atom, have been found to react with formamides by way of a Peterson reaction to form enamines. Trimethylsilylmethylbenzene behaved similarly. The enamines prepared from Nb-formy]-M',Nb-dimethyltryptamine cyclized readily to P-carbolines. The reaction of formamides with lithiated 4-methylpyridines as a route to enamines was examined but proved to be less general and proceeded in lower yield than the route by way of the Peterson reaction. The nuclear magnetic resonance and mass spectra of the enamines and P-carbolines derived from 3 are discussed.RAHUL VOHRA et DAVID B. MACLEAN. Can. J. Chem. 72, 1660 (1994).On a trouvC que les pyridines et benzopyridines substituies par des groupes trimCthylsilylmCthyles en CY ou en y de I'azote rCagissent avec les formamides, par le biais d'une reaction de Peterson, pour conduire h la formation dlCnamines. Le trimCthy1-silylmCthylbenzi?ne se comporte de la mzme manicre. Les Cnamines prCparCes partir de la Nb-formy]-Na,Nb-dimethyltryptamine se cyclisent facilement en P-carbolines. On a examin6 la rkaction des formamides avec les 4-mtthylpyridines lithiCes, comme voie d'acccs aux Cnamines, mais on a montrk que la rkaction est moins gCnCrale et qu'elle se produit avec un rendement plus faible que la voie impliquant la reaction de Peterson. On discute des spectres de rCsonance magnCtique nuclkaire et de masse des Cnamines et des P-carbolines dCrivCs du produit 3.[Traduit par la rkdaction]

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Section: Enamines By Reaction Of Lithiated Methyl Pyridines Withmentioning

confidence: 99%

Enamines from formamides. Synthesis of 1,2,3,4-tetrahydro-1-substituted β-carbolines

Vohra¹,

MacLean²

1994

Can. J. Chem.

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“…As already mentioned, the parent cyclophanes with an unsaturated, non-aromatic bridge (9,11,27) are all quite unstable compounds. It is well known from the chemical literature [36] that benzannelation often increases the stability of reactive compounds dramatically, and we therefore decided to prepare the 1,2-diethynylbenzene bridged derivative 34.…”

Section: Resultsmentioning

confidence: 99%

Preparation, Structural Properties and Thermal Isomerization of Hex‐3‐ene‐1,5‐diyne Bridged [2.2]Paracyclophanes

Dix

Bondarenko

Jones

et al. 2014

Chemistry A European J

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The [2.2]paracyclophane moiety is used as a spacer to connect the ends of a hex-3-ene-1,5-diyne unit, a π-system that on thermolysis usually cycloaromatizes to a benzene ring (Bergman cyclization). For the preparation of the pseudo-geminally-bridged system 9, the diacetylene 3 was chain-extended to the diol 16, which after conversion to the pseudo-geminal dibromide 17 was ring-closed by treatment with LiHMDS/HMPA to the [2.2]paracyclophane enediyne 9. Whereas the McMurry coupling of the pseudo-ortho bisaldehyde 24 resulted in the formation of the hexadienyne-bridged cyclophane 27, the pseudo-ortho-bridged hydrocarbon 11 was obtained by preparing first the diol 28 from 24, converting the latter into the dioxolane 29, which in the last step furnished the olefin 11 by treatment with Tf2 O/EtN(iPr)2 . The authentic Bergman product 10 of the pseudo-gem-bridged hexenediyne 9 was synthesized by a conventional sequence starting from the ethynyl formyl substrate 18. Since the pseudo-ortho-enediyne-bridged hydrocarbon 11 is thermally labile, its benzannelated derivate 34 was prepared. No classical Bergman cyclization reactions could be observed for any of the [2.2]paracyclophane-bridged hexenediynes prepared here. In the pseudo-gem-series the fulvenes 14 and 15 were the only products that could be identified under thermal conditions (McMurry coupling); the benzannelated substrate 34 gave the benzofulvene-bridged cyclophane 36 on photolysis. Bergman cyclizations yielding fulvene derivatives are extremely rare. The mechanism of the cyclization of 9 and 34 is discussed, using compliance constants. The structure assignments of the hydrocarbons synthesized in this study are based on spectroscopic studies as well as X-ray structural analyses for 9, 10, 11, 27, and 34.

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“…Recrystallisation of this material by slow evaporation of a 1: 9,151.6,149.7,149.5,148.7,148.4,147.0,136.1,134.4,134.3,133.8,131.3,129.6,73.0,72.9,60.9,60.6,31.7,30.1,29.7,27.6,26.6,26.3,25.6,25.2,24.2,22.5,22.4,H 8.45,N 7.43,O 5.09;found C 79.35,H 8.68,N 7.27,; m/z (%): 964 (100) [MNa ϩ ], 980 (7) [MK ϩ ]. (3-tert-Butoxypropyl)-1,2,3,4,4,6,7,8-octahydro-4 8,138.4,136.7,129.6,128.0,126.4,126.0,72.7,61.1,29.4,27.7,27.6,26.2,25.0,H 8.23,N 2.93,O 3.35;found C 85.53,H 8.16,N 3 Butoxypropyl)-1,2,3,6,7,8-hexahydroacridine-4,5-dione (17): A solution of 9.57 g (20 mmol) of 16 in 400 mL of CH 2 Cl 2 / methanol (1:1, v/v) was cooled to -78°C. An ozone/oxygen mixture was bubbled through the solution for 4 h and then the solution was purged of ozone by bubbling wi...…”

Section: Methods Bmentioning

confidence: 99%

“…- 13 C NMR (CDCl 3 ): δ ϭ 195. 8,156.0,151.2,150.4,148.3,147.3,147.0,146.3,138.3,135.8,134.1,133.5,132.9,130.3,129.4,128.2,72.6,72.5,39.0,32.6,29.7,27.6,27.4,27.0,26.0,25.9,25.1,24.8,24.3,23.2,23.0,22.6,H 8.48,N 6.43,O 9.79;found C 75.15,H 8.28,N 6.41,NH 3…”

Section: Heptacyclic Ketone 14mentioning

confidence: 99%

“…[7] Conversion into the butanal 3 was achieved in 84% yield on a large scale by formylation of its corresponding Grignard reagent using N-formylpiperidine as a formylating agent. [8] 8-(3-tert-Butoxypropyl)-2hydroxytricyclo[7.3.1.0 2,7 ]tridecan-13-one (4) was prepared in 87% yield by the aldol condensation of cyclohexanone with 3. [9] The structure of 4 was confirmed by X-ray analysis and is shown in Figure 3.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of New Soluble Annelated Polypyridines

Aït‐Haddou¹,

Fontenas

Bejan

et al. 2000

Eur. J. Org. Chem.

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Aldehydes by Formylation of Grignard or Organolithium Reagents with N‐Formylpiperidine

Cited by 78 publications

References 8 publications

Enamines from formamides. Synthesis of 1,2,3,4-tetrahydro-1-substituted β-carbolines

Enamines from formamides. Synthesis of 1,2,3,4-tetrahydro-1-substituted β-carbolines

Preparation, Structural Properties and Thermal Isomerization of Hex‐3‐ene‐1,5‐diyne Bridged [2.2]Paracyclophanes

Synthesis of New Soluble Annelated Polypyridines

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