Scaffold Diversity from <i>N</i>-Acyliminium Ions

Wu, Peng; Nielsen, Thomas E.

doi:10.1021/acs.chemrev.6b00806

Cited by 171 publications

(102 citation statements)

References 258 publications

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“…For a review article by G. Stucky 'Elektrochemische Oxidation von Carbonsäuren zur Synthese enantiomerenreiner Verbindungen', see ref [28]. 4 For two recent, more or less randomly picked review articles on N-acyliminium ions in organic synthesis see ref [29,30]. and references cited therein.…”

mentioning

confidence: 99%

Preparation of Enantiomerically Pure Compounds Employing Anodic Oxidations of Carboxylic Acids – A Late Review of Research Done in the 1980ies

Seebàch

2019

Helvetica Chimica Acta

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There are widely unknown enantiopure building blocks and non‐conventional transformations described in this old work that could become useful in today's diversity‐oriented organic synthesis world. Coupling and mixed couplings of functionalized CF3‐substituted chiral radicals by Kolbe electrolysis of carboxylic acids lead to hexafluoro‐hexane‐2,5‐diol and to butyro‐ and valerolactone derivatives with functional‐group relationships that normally require components with reactivity umpolung. Oxidative decarboxylation of amino‐acid and peptide derivatives by Hofer‐Moest electrolyses provide entry into the synthetic use of chiral acyliminium‐ion intermediates. Chiral oxazoline and thioazoline building blocks (from serine, threonine, and cysteine) are accessible for substitutions and cycloadditions. The stereochemical course of oxidative CO2H replacement in serine by nucleophilically introduced groups with retention of configuration is discussed.

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confidence: 99%

Preparation of Enantiomerically Pure Compounds Employing Anodic Oxidations of Carboxylic Acids – A Late Review of Research Done in the 1980ies

Seebàch

2019

Helvetica Chimica Acta

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“…We conceived that under acidic conditions cyclic sulfonyliminium ion 5 would form upon the elimination of water from 3 [14] and could be trapped by alcohols to afford hemiaminal ethers 6 (pathway ai nF igure 2a). We conceived that under acidic conditions cyclic sulfonyliminium ion 5 would form upon the elimination of water from 3 [14] and could be trapped by alcohols to afford hemiaminal ethers 6 (pathway ai nF igure 2a).…”

mentioning

confidence: 99%

Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System

Zha

et al. 2018

Angewandte Chemie

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Axial chirality is ap revalent and important phenomenon in chemistry.H erein we report ac ombination of dynamic covalent chemistry and axial chirality for the development of av ersatile platform for the binding and chirality sensing of multiple classes of mononucleophiles.A ne quilibrium between an open aldehyde and its cyclic hemiaminal within biphenyl derivatives enabled the dynamic incorporation of ab road range of alcohols,t hiols,p rimary amines,a nd secondary amines with high efficiency.S electivity toward different classes of nucleophiles was also achieved by regulating the distinct reactivity of the system with external stimuli. Through induced helicity as aresult of central-to-axial chirality transfer,t he handedness and ee values of chiral monoalcohol and monoamine analytes were reported by circular dichroism. The strategies introduced herein should find application in many contexts,including assembly,sensing, and labeling.Axial chirality arises from the nonplanar arrangement of substituents about ac hiral axis, [1] such as the aryl-aryl bond within atropisomeric biaryl compounds, [2] which is of significant importance in the research areas of asymmetric catalysis, natural products,s upramolecular assemblies,a nd organic materials. [3] Despite the long history of exploring axial chirality,t here is continued interest in discovering novel strategies for communication between central and axial chirality. [1][2][3] Fore xample,l ight-or chemical-fuel-driven unidirectional molecular motors have been created through the control of rotamers. [4] Moreover,t he chirality of metalorganic or organic frameworks and cages has been modulated through the incorporation of atropisomeric motifs. [5] Atropisomeric receptors have also been used in av ariety of analytical applications, [6] such as chiroptical assays for enantiomeric composition, [7] which can be employed to rapidly analyze chiral samples for catalyst development. Them anipulation of axial chirality in af acile,d ynamic,a nd versatile fashion could find broad application.Reversible covalent bonding has had asignificant impact on the field of supramolecular chemistry, [8] in which the coupling and exchange of specific functional groups through dynamic covalent reactions (DCRs) can lead to systematic chemical diversity and complexity. [9] Monofunctionalities, such as monoamines and monoalcohols,a re among the most used building blocks and are among the most sought after targets in asymmetric catalysis.A sc ompared to imine formation with chiral primary amines, [10] dynamic covalent bonding and sensing systems for sterically hindered chiral secondary monoamines are nearly non-existent. [11] Furthermore,d ue to the poor nucleophilicity of alcohols,r eceptors that bind chiral mono-ols also remain scarce. [12] We have been seeking ag eneral strategy based on the use of ac ommon receptor capable of recognition, coupled with amechanism to optically report chirality,for multiple classes of monodentate organic functional groups.Building on the dynamic covalent c...

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“…Our reactiond esign combines a Mukaiyama-Manniche ventt os et the keyo xocarbenium intermediate II, [6,7] along with first use of at ertiary enamide functionality [5,8,9] as the central dipolara lkene. [10] Upon generating an N-acyliminium ion III, [11,12] which is efficiently trapped by an enoxysilane in the terminatings tep of the catalytic cycle( Scheme 1, d), [13,14] the tertiaryenamide acts as the expected 1,2-dipole. [9] This Mukaiyama-Mannich-Prins cascade transformation operates through an uncommon multi-step catalytic cycle which reveals sequentially two N-acyliminium I and III and one silyloxycarbenium II intermediates, providing us with an unusual hybrid Prins/aza-Prins [15][16][17][18] approach(Scheme1,c and d).…”

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confidence: 99%

Novel Hybrid Prins/Aza‐Prins Oxocarbenium/N‐Acyliminium Cascade: Expedient Access to Complex Indolizidines

Berthet

Beauseigneur

Moine

et al. 2018

Chemistry A European J

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Heavy silyl enol ethers (mostly TIPS and TBS) combine with cyclic N-alkenyl N-acyliminium salts generated in situ from their N,O-acetal precursors, to furnish highly functionalized indolizidines through an unprecedented double Mukaiyama-Mannich-Prins cascade transformation. This novel cascade annulation process demonstrates a promising scope, and takes place mostly catalytically with interesting stereocontrol. Furthermore, an appealing facet of this chemistry is emphasized with a bicatalytic approach by which the Mannich-Prins cascade follows a Ru-catalyzed N-allylamide to N-(E)-propenyl isomerization of the aminal counterpart in a one-pot operation.

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Scaffold Diversity from N-Acyliminium Ions

Cited by 171 publications

References 258 publications

Preparation of Enantiomerically Pure Compounds Employing Anodic Oxidations of Carboxylic Acids – A Late Review of Research Done in the 1980ies

Preparation of Enantiomerically Pure Compounds Employing Anodic Oxidations of Carboxylic Acids – A Late Review of Research Done in the 1980ies

Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System

Novel Hybrid Prins/Aza‐Prins Oxocarbenium/N‐Acyliminium Cascade: Expedient Access to Complex Indolizidines

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