Rearrangement of quinine in superacid: an efficient access to a novel chiral heterocyclic system

Thibaudeau, Sébastien; Violeau, Bruno; Martin‐Mingot, Agnès; Jouannetaud, Marie‐Paule; Jacquesy, Jean‐Claude

doi:10.1016/s0040-4039(02)02068-3

Cited by 21 publications

(8 citation statements)

References 19 publications

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“…This behaviour of amino alcohols in superacid led to the synthesis of a novel chiral heterocyclic system starting from quinine in superacid. 22 No similar effect was observed on the hydrofluorination reaction. Amino alcohol 1d and amino ether 1e yielded corresponding fluoroamines (Table 1, entries 4 and 5), and no other products resulting from intramolecular nucleophilic attack were detected in the crude mixture.…”

Section: Nitrogen Substitution Effect On the Hydrofluorination Reactionmentioning

confidence: 96%

Substitution effect on the hydrofluorination reaction of unsaturated amines in superacid HF/SbF5

Liu¹,

Martin‐Mingot²,

Jouannetaud³

et al. 2009

Org. Biomol. Chem.

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This paper describes the scope and limitations of the hydrofluorination reaction in superacid HF/SbF(5). On the basis of experimental studies of polyfunctional substrates' behaviour, the dramatic effect of substitution on the superelectrophilic character of ammonium-carbenium dications was emphasized. This reaction was applied to the synthesis of novel fluorinated key building blocks. Furthermore, the hydrofluorination reaction and the discovered homodimerization/fluorination reaction were applied to the synthesis of highly valued fluorinated diamines.

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Section: Nitrogen Substitution Effect On the Hydrofluorination Reactionmentioning

confidence: 96%

Substitution effect on the hydrofluorination reaction of unsaturated amines in superacid HF/SbF5

Liu¹,

Martin‐Mingot²,

Jouannetaud³

et al. 2009

Org. Biomol. Chem.

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“…We found that when quinine is heated in 28 eq. of CF 3 SO 3 H at 50°C for 24 h and then at 80°C for 15 h, successive rearrangements [23][24][25] accompanied by demethylation occur to generate α-ICPN. The nuclear Overhauser effect spectroscopy (NOESY) spectrum and X-ray crystallography 26) of α-ICPN indicates that it takes an anti conformation where the nucleophilic nitrogen faces toward the phenolic hydroxy group like β-ICD.…”

Section: Asymmetric Morita-baylis-hillman Reactionmentioning

confidence: 99%

Total Synthesis of Biologically Active Natural Products Based on Highly Selective Synthetic Methodologies

Hatakeyama

2014

CHEMICAL & PHARMACEUTICAL BULLETIN

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Total syntheses of structurally and biologically intriguing natural products relying on new synthetic methodologies are described. This article features cinchona alkaloid-catalyzed asymmetric Morita-BaylisHillman reactions, heterocycle syntheses based on rhodium-catalyzed C-H amination and indium-catalyzed Conia-ene reactions, and their utilization for the syntheses of the phoslactomycin family of antibiotics, glutamate receptor agonists and antagonists, and alkaloids with characteristic highly substituted pyrrolidinone core structures.

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“…For example, quinine ( 122 ) gives product 123 in 89% yield from reaction with HF-SbF 5 at −30 °C (Scheme 25) [38]. The conversion is thought to involve the di- and triprotonated derivatives of quinine 124 and 125 .…”

Section: Reviewmentioning

confidence: 99%

“…Jacquesy and coworkers have examined the chemistry of natural products in superacids and found several unusual rearrangements of multiply-protonated species. For example, quinine ( 122 ) gives product 123 in 89% yield from reaction with HF-SbF 5 at −30 °C ( Scheme 25 ) [ 38 ]. The conversion is thought to involve the di- and triprotonated derivatives of quinine 124 and 125 .…”

Section: Reviewmentioning

confidence: 99%

Molecular rearrangements of superelectrophiles

Klumpp¹

2011

Beilstein J. Org. Chem.

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SummarySuperelectrophiles are multiply charged cationic species (dications, trications, etc.) which are characterized by their reactions with weak nucleophiles. These reactive intermediates may also undergo a wide variety of rearrangement-type reactions. Superelectrophilic rearrangements are often driven by charge–charge repulsive effects, as these densely charged ions react so as to maximize the distances between charge centers. These rearrangements involve reaction steps similar to monocationic rearrangements, such as alkyl group shifts, Wagner–Meerwein shifts, hydride shifts, ring opening reactions, and other skeletal rearrangements. This review will describe these types of superelectrophilic reactions.

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Rearrangement of quinine in superacid: an efficient access to a novel chiral heterocyclic system

Cited by 21 publications

References 19 publications

Substitution effect on the hydrofluorination reaction of unsaturated amines in superacid HF/SbF5

Substitution effect on the hydrofluorination reaction of unsaturated amines in superacid HF/SbF5

Total Synthesis of Biologically Active Natural Products Based on Highly Selective Synthetic Methodologies

Molecular rearrangements of superelectrophiles

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