A new efficient synthesis of β-aminoketones via Δ4-isoxazolines.

Mancuso, Vincent; Hootelé, Claude

doi:10.1016/s0040-4039(00)82225-x

Cited by 22 publications

(7 citation statements)

References 9 publications

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“…On the other hand, the cycloadditions are highly regioselective, the electron-with- reactivity and the observed regioselectivity are in agreement SCHEME 1 with previous observations and theoretical predictions (2,8). According to Houk's perturbation treatment of 1,3-dipolar ~~~~~~~~i~ nitrone-alkene 1,3-dipolar cycloadditions cycloadditions, the preferred regioisomer will arise from the involving either ,-hiral nitrones or ,-.,iral alkenes have received transition state in which the atoms with the largest orbital coefattention: high asymmetric induction has been observed, for ficients interact, i.e., the transition state in which the carbon of example, in the condensation of nitrones with alkenyl sulfoxthe nitrone moiety becomes bonded to the carbon of the dipoides (4) or, very recently, with chiral ally1 ethers (5).…”

Section: Introductionsupporting

confidence: 91%

Synthesis of enantiomeric β-amino ketones via 1,3-dipolar cycloaddition and chromatographic resolution

Louis¹,

Mill²,

Mancuso³

et al. 1994

Can. J. Chem.

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. 72, 1347 (1994). The cycloaddition reactions of 3,4,5,6-tetrahydropyridine I-oxide 1 with the homochiral alkynyl sulfoxides 60-e proceed in high yield to afford, with low asymmetric induction, mixtures of diastereomeric isoxazolines that are readily separated by column chromatography. ' The resolved isoxazolines can be subsequently converted, by hydrogenolysis, to enantiomeric p-amino ketones.CHANTAL LOUIS, SIBEL MILL, VINCENT MANCUSO et CLAUDE HOOTEL~. Can. J. Chem. 72, 1347Chem. 72, (1994. Les rCactions de cycloaddition entre la 3,4,5,6-tktrahydropyridine I-oxyde 1 et les sulfoxydes acCtylCniques homochiraux 6a-e conduisent avec de bons rendements et une induction asymetrique faible a des mtlanges d'isoxazolines diasttrtoisom&res facilement sCparables par chromatographie sur colonne. Les isoxazolines rCsolues peuvent &tre converties, par hydrogtnolyse, en p-aminocCtones Cnantiomkres.[Traduit par la RCdaction] Introduction ene (6) (Scheme 2). Based on the fact that Grignard reactions p -~~i~~ ketones an important ,-lass o~c o m p o u n~s with chiral sulfinate esters proceed stereospecifically with for which the synthesis deserves interest. In this regard, we preinversion of configuration at the sulfur atom (7), the acet~lenic viously reported a new efficient synthesis based on the observasulfoxides 6a-e are assigned the S configuration; the optical tion that 4-isoxazolines 3 can be viewed as masked p-amino purity and the absolute configuration of 6c-e were previously ketones, which could be released by hydrogenolysis of the confirmed by their conversion into the corresponding alkenyl N-0 bond (1) (Scheme 1). Although 4-isoxazolines have derivatives (6).2 proven to be thermally labile heterocycles and display an arrayThe reaction nitrone 1 with the alkynyl sulfoxides 6a-e of rearrangements (2, 31, we established that under carefully gave mixtures of the diastereomeric isoxazolines 7a-e and 8a-e controlled conditions they can be prepared in good yield by (Scheme 3); the large differences in the R,s allowed the comnitrone-alkyne cycloaddition. ~~~~~~~ of the N-0 plete separation of the individual diastereomers of each pair by bond can be performed by hydrogen in the presence of P d C .flash chromatography silica gel. Typical results are PreApplication of this procedure to the synthesis of sented in and deserve some 2-phenacylpiperidine, for example (4, R = C6H,), proceedsAll the cycloadditions proceed with excellent yields. It from nitrone 1 and pheny lacety lene with 70% overall yield. In

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Section: Introductionsupporting

confidence: 91%

Synthesis of enantiomeric β-amino ketones via 1,3-dipolar cycloaddition and chromatographic resolution

Louis¹,

Mill²,

Mancuso³

et al. 1994

Can. J. Chem.

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“…12 Hydrogenation of fused 4 isoxazolines 36 at a less ac tive catalyst yields the corresponding β amino ketones 37 (see Refs 41 and 47) or products of their intramolecular cyclization (38) (Scheme 13). 41 Amino ketones 40 ob tained by reduction of 4 isoxazolines 39 with molecular hydrogen on Pt also undergo intramolecular cyclization into compounds 41 (see Scheme 13). 42 In some cases, the reduction with hydrogen on plati num gives amino alcohols 42 (Scheme 14).…”

Section: Methodsmentioning

confidence: 99%

The chemistry of 2,3-dihydroisoxazole derivatives

Чуканов

Резников

2011

Russ Chem Bull

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“…[67] Reduction of 4-isoxazoles can lead to β-amino ketones or β-amino alcohols. [68][69][70] Hootelé et al reported that β-amino ketones are obtained in good yields by hydrogenolysis in the presence of Pd/C in ethanol (e.g., 167, Scheme 39). [68] Hydrogenolysis of 4-isoxazolines has also been used to prepare β-amino ketones, which are key intermediates in the reported synthesis of tetraponerine alkaloids.…”

Section: -Isoxazolines As Building Blocks For Acyclic Compoundsmentioning

confidence: 99%

“…[68][69][70] Hootelé et al reported that β-amino ketones are obtained in good yields by hydrogenolysis in the presence of Pd/C in ethanol (e.g., 167, Scheme 39). [68] Hydrogenolysis of 4-isoxazolines has also been used to prepare β-amino ketones, which are key intermediates in the reported synthesis of tetraponerine alkaloids. [69] The synthesis of β-amino ketones from the 4-isoxazolines 168 (R 2 ϶ Ph, Scheme 39) upon treatment with a suspension of Zn powder in glacial acetic acid has also been reported.…”

Section: -Isoxazolines As Building Blocks For Acyclic Compoundsmentioning

confidence: 99%