Rapid and Stereoselective Synthesis of Spirocyclic Ethers via the Intramolecular Piancatelli Rearrangement

Palmer, Leoni I.; Alaniz, Javier Read de

doi:10.1021/ol303263q

Cited by 82 publications

(36 citation statements)

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“…15 Based on our success with the aza-Piancatelli rearrangement, we sought the use of alcohols as nucleophiles. 16 Prior to our report, there were no examples of an oxaPiancatelli reaction. Here, we built substrates that had varying substitutions of the furylcarbinol (Scheme 7) as well as including the use of tethers containing primary, secondary and tertiary alcohols.…”

Section: Scheme 5 Synthesis Of An Hnk 1 Antagonistmentioning

confidence: 84%

“…To our delight, the rearrangement was efficient, trans-selective and amenable to a wide range of substitutions both on the aniline and on the furylcarbinol. 10 We were most encouraged by this initial study, that demonstrates that electron-rich, electron-poor, sterically bulky and even secondary anilines (16) 3 and La(OTf) 3 could also be used to catalyze the aza-Piancatelli reaction. 11…”

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confidence: 99%

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Lewis Acid Catalyzed Rearrangement of Furylcarbinols: The Aza- and Oxa-Piancatelli Cascade Reaction

Palmer¹,

Alaniz²

2013

Synlett

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Section: Scheme 5 Synthesis Of An Hnk 1 Antagonistmentioning

confidence: 84%

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confidence: 99%

Lewis Acid Catalyzed Rearrangement of Furylcarbinols: The Aza- and Oxa-Piancatelli Cascade Reaction

Palmer¹,

Alaniz²

2013

Synlett

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“…The mechanism of the reaction might be explained on the basis of generation of the oxonium cationic species (II) through TiBr 4 ‐mediated formation of complex (I) with secondary OBn group, as described in Scheme 30. Rearomatization of the furanoid ring and subsequent tautomerization afforded α,β‐unsaturated 1,5‐dicarbonyl derivative 6 .…”

Section: Resultsmentioning

confidence: 99%

Gold(III) Chloride Catalyzed Synthesis of Chiral Substituted 3‐Formyl Furans from Carbohydrates: Application in the Synthesis of 1,5‐Dicarbonyl Derivatives and Furo[3,2‐c]pyridine

Mal

Sharma

Das

2014

Chemistry A European J

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This report describes a gold(III)-catalyzed efficient general route to densely substituted chiral 3-formyl furans under extremely mild conditions from suitably protected 5-(1-alkynyl)-2,3-dihydropyran-4-one using H2 O as a nucleophile. The reaction proceeds through the initial formation of an activated alkyne-gold(III) complex intermediate, followed by either a domino nucleophilic attack/anti-endo-dig cyclization, or the formation of a cyclic oxonium ion with subsequent attack by H2 O. To confirm the proposed mechanistic pathway, we employed MeOH as a nucleophile instead of H2 O to result in a substituted furo[3,2-c]pyran derivative, as anticipated. The similar furo[3,2-c]pyran skeleton with a hybrid carbohydrate-furan derivative has also been achieved through pyridinium dichromate (PDC) oxidation of a substituted chiral 3-formyl furan. The corresponding protected 5-(1-alkynyl)-2,3-dihydropyran-4-one can be synthesized from the monosaccharides (both hexoses and pentose) following oxidation, iodination, and Sonogashira coupling sequences. Furthermore, to demonstrate the potentiality of chiral 3-formyl furan derivatives, a TiBr4 -catalyzed reaction of these derivatives has been shown to offer efficient access to 1,5-dicarbonyl compounds, which on treatment with NH4 OAc in slightly acidic conditions afforded substituted furo[3,2-c]pyridine.

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“…Read de Alaniz also explored the oxa-Piancatelli version of the rearrangement on substrates bearing a hydroxy-alkyl moiety at the 5 position of the furan ring (3, see Scheme 5, and 48) [57] and thereby accessing oxaspirocycles (49 and 50) (Scheme 20) in only one step and in a highly diasteroselective manner, thus avoiding the usually performed multistep procedures [58][59][60]. PhMe 80 °C…”

Section: Intramolecular Oxa-piancatelli Rearrangementmentioning

confidence: 99%

The Piancatelli Rearrangement: New Applications for an Intriguing Reaction

2013

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Nearly forty years ago, at the University of Rome, Giovanni Piancatelli and co-workers discovered the acid-catalyzed water-mediated rearrangement of 2-furylcarbinols into 4-hydroxycyclopentenones. These motifs are core components of several pharmacologically active compounds and precursors of many natural products. The main features of this reaction are the simple experimental conditions, the stereochemical outcome and the generality of the procedure. Consequently, a re-emergence of this reaction has been seen recently, including developments of the Piancatelli rearrangement with some interesting inter-and intramolecular variants. This review will mainly focus on the general aspects of the reaction along with its more recent applications.

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Rapid and Stereoselective Synthesis of Spirocyclic Ethers via the Intramolecular Piancatelli Rearrangement

Cited by 82 publications

References 41 publications

Lewis Acid Catalyzed Rearrangement of Furylcarbinols: The Aza- and Oxa-Piancatelli Cascade Reaction

Lewis Acid Catalyzed Rearrangement of Furylcarbinols: The Aza- and Oxa-Piancatelli Cascade Reaction

Gold(III) Chloride Catalyzed Synthesis of Chiral Substituted 3‐Formyl Furans from Carbohydrates: Application in the Synthesis of 1,5‐Dicarbonyl Derivatives and Furo[3,2‐c]pyridine

The Piancatelli Rearrangement: New Applications for an Intriguing Reaction

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