Cascade rearrangement of furylcarbinols with hydroxylamines: practical access to densely functionalized cyclopentane derivatives

Veits, Gesine K.; Wenz, Donald R.; Palmer, Leoni I.; Amant, André H. St.; Hein, Jason E.; Alaniz, Javier Read de

doi:10.1039/c5ob00944h

Cited by 35 publications

(21 citation statements)

References 46 publications

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“…Developing a method to easily introduce derivatives of p ‐anisidine is quite valuable because secondary amines can be generated in high yield after cleaving the p ‐methoxyphenyl group using cerium ammonium nitrate (CAN) (Scheme ). It is noteworthy that this deprotection is even compatible in the presence of a hydrogen α to the ketone, which was not possible according to the precedent report by the Read de Alaniz group using hydroxylamines . This approach also counterbalances the drawback that simple alkylamines, such as benzylamine, are unreactive in HFIP.…”

Section: Resultsmentioning

confidence: 97%

Harnessing the Lewis Acidity of HFIP through its Cooperation with a Calcium(II) Salt: Application to the Aza‐Piancatelli Reaction

Lebœuf

Marin

Michelet

et al. 2016

Chemistry A European J

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A method to extend the scope of the aza-Piancatelli reaction between 2-furylcarbinols and anilines is depicted. We found that 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) is the solvent of choice for this transformation, as it outcompetes the usual solvents in terms of rate and yield. Side reactions and other issues raised by the title reaction are prevented, thereby providing an avenue to complex molecules that were previously inaccessible. Lewis acidity studies and computations were carried out to unveil the role of HFIP. Based on these results, we propose that HFIP is, in fact, acting as a Lewis acid and that its acidity can be enhanced when combined with a calcium(II) salt.

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Section: Resultsmentioning

confidence: 97%

Harnessing the Lewis Acidity of HFIP through its Cooperation with a Calcium(II) Salt: Application to the Aza‐Piancatelli Reaction

Lebœuf

Marin

Michelet

et al. 2016

Chemistry A European J

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“…alkyl amines), were also tolerated in this variant. Finally the intramolecular variant was performed to obtain spyrocyclic CP 186 in good yield …”

Section: Piancatelli Rearrangementmentioning

confidence: 99%

“… Reaction scope of the Dy(OTf) 3 ‐promoted aza‐Piancatelli rearrangement of 2‐furylcarbinols with hydroxylamines affording CP 167 – 186 …”

Section: Piancatelli Rearrangementmentioning

confidence: 99%

“…Accordingly, the diastereoselective reduction of 167 and derivatives under modified Luche conditions followed by N−O bond cleavage using Zn/HCl afforded cyclopentanols 190 – 193 in moderate to good yields (Scheme ). Finally, it was demonstrated that oxidation of 190 into the 4‐amino‐CP 187 is possible using PDC, although with formation of the corresponding 2,4‐isomer 188 (Scheme ) …”

Section: Piancatelli Rearrangementmentioning

confidence: 99%

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Synthesis and Applications of Stenhouse Salts and Derivatives

Gomes

Coelho

Afonso

2018

Chemistry A European J

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In recent years, Stenhouse salts have attracted much attention as intermediates for the synthesis of cyclopenten-2-enones. This Minireview aims to present an overview of the methods for preparation, further transformation and applications of Stenhouse and Stenhouse-like salts. In this context, the Piancatelli rearrangement and its variants, and the recently reported donor-acceptor Stenhouse salts (DASA) will be addressed. The photophysical properties of DASA and its applications in colorimetric detection of amines, functionalization of polymers for detection of heat and nerve agents, photolithography and orthogonal photoswitching systems are discussed.

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“…The development, scope, and diverse synthetic utility of this newly developed rearrangement using non-aniline nucleophiles was investigated by Read de Alaniz and co-workers and is described in a companion paper. 24 ■ RESULTS AND DISCUSSION Description of Sampling Apparatus. In this article, we report the detailed kinetic behavior of the catalytic pathway with data acquired using a prototype apparatus capable of rapid parallel reaction analysis (for a detailed description, see SI.…”

Section: ■ Introductionmentioning

confidence: 99%

Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement

Chung

Thai

et al. 2015

ACS Catal.

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Continuing developments in the elucidation techniques of complex catalytic processes is of foremost importance to modern synthetic chemistry, and the identification of efficient synthetic techniques relies on precise, reliable, and adaptable methods to dissect the mechanism of a given transformation. Currently, methods of reaction development are grounded upon the systematic modification of specific variablessuch as temperature, time, concentration, etc.to account for and control the dynamic series of coupled equilibria within a catalytic environment. On the other hand, tandem reaction analytical methods that involve the concomitant use of different instruments to probe a reaction can provide time-resolved information regarding active chemical species and facilitate the interrogation and optimization of the system. Herein, we report our study applying tandem in situ ReactIR and HPLC-MS monitoring to the dysprosium(III) triflate-catalyzed aza-Piancatelli rearrangement of 2-furylcarbinols, a reaction that grants access to trans-4,5-disubstituted cyclopentenonescommon motifs in important biologically relevant and natural compounds. With a prototype automated sampling apparatus, information was obtained about the intrinsic chemoselectivity of the reaction, and previously unseen intermediates were observed, allowing for a more detailed reaction mechanism to be substantiated. The advantages of applying this type of tandem measurement to study these types of systems are also discussed.

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Cascade rearrangement of furylcarbinols with hydroxylamines: practical access to densely functionalized cyclopentane derivatives

Abstract: The aza-Piancatelli rearrangement with hydroxylamines to 4-aminocyclopentenones is described. Subsequent transformations highlight the versatility of the cyclopentene scaffold and the value of the hydroxylamine in this transformation.

Cited by 35 publications

References 46 publications

Harnessing the Lewis Acidity of HFIP through its Cooperation with a Calcium(II) Salt: Application to the Aza‐Piancatelli Reaction

Harnessing the Lewis Acidity of HFIP through its Cooperation with a Calcium(II) Salt: Application to the Aza‐Piancatelli Reaction

Synthesis and Applications of Stenhouse Salts and Derivatives

Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement

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