Triazole‐Based Anion‐Binding Catalysis for the Enantioselective Dearomatization of <i>N</i>‐Heteroarenes with Phosphorus Nucleophiles

Fischer, Tatjana; Duong, Qui‐Nhi; Mancheño, Olga Garcı́a

doi:10.1002/chem.201605660

Cited by 62 publications

(28 citation statements)

References 67 publications

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“…HBr was used more occasionally to hydrolyze phosphonates [ 124 – 126 ]. Regarding the nature of the alkyl chains of dialkyl phosphonates, it must be noted that most of the time these chains are methyl, ethyl, isopropyl or, occasionally, n -butyl [ 127 ]. This observation is likely explained by the synthetic methods employed to prepare phosphonates that frequently made use of the Arbuzov reaction [ 128 ] involving the commercially available trimethyl, triethyl or triisopropyl phosphite [ 129 ].…”

Section: Reviewmentioning

confidence: 99%

Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

138

103

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The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

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Section: Reviewmentioning

confidence: 99%

Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

138

103

View full text Add to dashboard Cite

show abstract

“…Scheme 3 depicts the synthetic route followed to incorporate a 1,2,3-triazole group as a connecting block within the organocatalytic system. According to previous reports, the triazole segment could act as a good hydrogen bond acceptor at the transition state of the aldol reaction increasing the rigidity of such transition state and in this way possibly increasing the stereoselectivity of the organocatalytic system [ 83 ]. In the present system, the triazole fragment was used as spacer and connector between the silica support and the prolinol group that is involved in enamine formation, since it was anticipated that this would enable hydrogen bond interactions to anchor electrophilic substrates during the aldol reaction [ 83 , 84 , 85 , 86 , 87 ].…”

Section: Resultsmentioning

confidence: 99%

New Mesoporous Silica-Supported Organocatalysts Based on (2S)-(1,2,4-Triazol-3-yl)-Proline: Efficient, Reusable, and Heterogeneous Catalysts for the Asymmetric Aldol Reaction

et al. 2020

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Novel organocatalytic systems based on the recently developed (S)-proline derivative (2S)-[5-(benzylthio)-4-phenyl-(1,2,4-triazol)-3-yl]-pyrrolidine supported on mesoporous silica were prepared and their efficiency was assessed in the asymmetric aldol reaction. These materials were fully characterized by FT-IR, MS, XRD, and SEM microscopy, gathering relevant information regarding composition, morphology, and organocatalyst distribution in the doped silica. Careful optimization of the reaction conditions required for their application as catalysts in asymmetric aldol reactions between ketones and aldehydes afforded the anticipated aldol products with excellent yields and moderate diastereo- and enantioselectivities. The recommended experimental protocol is simple, fast, and efficient providing the enantioenriched aldol product, usually without the need of a special work-up or purification protocol. This approach constitutes a remarkable improvement in the field of heterogeneous (S)-proline-based organocatalysis; in particular, the solid-phase silica-bonded catalytic systems described herein allow for a substantial reduction in solvent usage. Furthermore, the supported system described here can be recovered, reactivated, and reused several times with limited loss in catalytic efficiency relative to freshly synthesized organocatalysts.

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“…However, the high water‐solubility of α‐aminomethylbisphosphonic acid derivatives made us discard these reaction conditions. The esterification reaction was carried out using trialkyl orthoformate derivatives as alkylating agents, which usually compare favourably with other procedures described in the literature , …”

Section: Resultsmentioning

confidence: 99%

1‐Aminovinylphosphonate Esters as Substrates for the Diels‐Alder Reaction: First Synthetic and Theoretical Study

et al. 2019

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The Diels‐Alder reaction of 1‐aminovinylphosphonate esters has been studied for the first time as a suitable procedure leading to quaternary carbocyclic α‐aminophosphonates. The reaction is influenced by steric effects at the phosphonate functionality (bulky groups hinder the reaction) and electronic effects at the amino group (electron‐withdrawing substituents increase the reaction rate). The exo/endo ratio is constant, and no influence of the solvent is observed. The experimental results have been rationalized by DFT methods.

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Triazole‐Based Anion‐Binding Catalysis for the Enantioselective Dearomatization of N‐Heteroarenes with Phosphorus Nucleophiles

Cited by 62 publications

References 67 publications

Phosphonic acid: preparation and applications

Phosphonic acid: preparation and applications

New Mesoporous Silica-Supported Organocatalysts Based on (2S)-(1,2,4-Triazol-3-yl)-Proline: Efficient, Reusable, and Heterogeneous Catalysts for the Asymmetric Aldol Reaction

1‐Aminovinylphosphonate Esters as Substrates for the Diels‐Alder Reaction: First Synthetic and Theoretical Study

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