Regioselective Synthesis of α- and <i>γ-</i>Amino Quinolinyl Phosphonamides Using <i>N</i>-Heterocyclic Phosphines (NHPs)

Shetty, Manasa; Huang, Hai; Kang, Jun Yong

doi:10.1021/acs.orglett.7b03829

Cited by 10 publications

(4 citation statements)

References 46 publications

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Section: Other Types Of Transition Metal-free Dearomatizationsmentioning

confidence: 99%

“…Kang and co-workers described the regioselective phosphonylation of quinolines mediated by N -heterocyclic phosphines (NHPs) ( Scheme 220 ). 293 The reaction of quinolines, chloroformates, and NHP-thiourea I in dichloromethane at 40 °C afforded α-amino quinolinyl phosphonamides 456 by means of a Reissert-type reaction ( Scheme 220 , eq 1). Quinoline derivatives containing electron-donating and electron-withdrawing groups at the 6-position efficiently afforded the corresponding α-amino quinolinyl phosphonamides in moderate to good yields with high regioselectivity.…”

Section: Addition Of Other Nucleophilesmentioning

confidence: 99%

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Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Escolano,

Gaviña,

Alzuet-Piña

et al. 2024

Chem. Rev.

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Dearomatization reactions have become fundamental chemical transformations in organic synthesis since they allow for the generation of three-dimensional complexity from two-dimensional precursors, bridging arene feedstocks with alicyclic structures. When those processes are applied to pyridines, quinolines, and isoquinolines, partially or fully saturated nitrogen heterocycles are formed, which are among the most significant structural components of pharmaceuticals and natural products. The inherent challenge of those transformations lies in the low reactivity of heteroaromatic substrates, which makes the dearomatization process thermodynamically unfavorable. Usually, connecting the dearomatization event to the irreversible formation of a strong C−C, C− H, or C−heteroatom bond compensates the energy required to disrupt the aromaticity. This aromaticity breakup normally results in a 1,2-or 1,4-functionalization of the heterocycle. Moreover, the combination of these dearomatization processes with subsequent transformations in tandem or stepwise protocols allows for multiple heterocycle functionalizations, giving access to complex molecular skeletons. The aim of this review, which covers the period from 2016 to 2022, is to update the state of the art of nucleophilic dearomatizations of pyridines, quinolines, and isoquinolines, showing the extraordinary ability of the dearomative methodology in organic synthesis and indicating their limitations and future trends.

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Section: Other Types Of Transition Metal-free Dearomatizationsmentioning

confidence: 99%

Section: Addition Of Other Nucleophilesmentioning

confidence: 99%

Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Escolano,

Gaviña,

Alzuet-Piña

et al. 2024

Chem. Rev.

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“…Utilizing N‐heterocyclic phosphines (NHPs) as the phosphorylation reagent, the Kang group recently develpoed a regioselective synthesis of α‐ or γ‐aminoquinolinyl phosphonamides via a 1,2‐ or 1,4‐phosphonation of quinolines (Scheme ) . The Brønsted acid motifs on the NHPs played a key role in the regioselectivity.…”

Section: Direct Phosphorylation Of the Parent Heterocyclesmentioning

confidence: 99%

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

2020

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Scheme 20. Phosphonation of pyridinones.Scheme 21. CuI-catalyzed phosphoramidate formation.Scheme22. Phosphonation of coumarin and quinolinone.Scheme23. Silver(I)-catalyzed phosphonation of coumarins. Scheme 33. Electrochemical C(sp 2 )ÀHphosphonation of quinoxaline-2(1H)-ones. Scheme 39. Phosphorylation of quinoxaline-2(1 H)-ones. Scheme40. Autoxidative phosphorylation of quinoxalines. Scheme 41. DTBP-mediated formation of phosphonated benzothiazoles. Scheme42. Phosphonation of imidazole[2,1-b]thiazoles.Scheme 47. Copper(I)-catalyzedp hosphonationo fN-iminoisoquinolinium ylides. Scheme48. Aerobic phosphonationofC ( sp 3 ) À Hbonds. Scheme 49. Copper(II)/PBQ-catalyzed phosphorylation of 3,4-dihydro-1,4-benzoxazin-2-ones. Scheme 87. Asymmetric exo-selective [3+ +2] cycloaddition to afford phosphorus-substituted pyrrolidines. Scheme 95. Cascade condensation/cyclization to phosphonylated thienopyridines. Scheme 96. S N Ar'-involved cascade reactions to phosphonylated oxygenorn itrogen heterocycles.Scheme 97. Manganese(III)-mediated synthesis of 3-phosphonyldihydrofuransfrom b-ketophosphonates.Scheme98. Cyclization to phosphonated isochromenes.Scheme 121. Asymmetric [4+ +2] cycloaddition of b,g-unsaturated a-ketophosphonates.

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“…Finally, the formation of lithium derivatives or Grignard reagents using aryl halides as substrates may be also employed [ 2 , 6 , 7 ]. In the past decade, interesting methods of nontypical specific procedures for the synthesis of heteroaromatic phosphonates have been studied and elaborated [ 12 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ].…”

Section: Introductionmentioning

confidence: 99%

One-Pot Phosphonylation of Heteroaromatic Lithium Reagents: The Scope and Limitations of Its Use for the Synthesis of Heteroaromatic Phosphonates

et al. 2023

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A one-pot lithiation–phosphonylation procedure was elaborated as a method to prepare heteroaromatic phosphonic acids. It relied on the direct lithiation of heteroaromatics followed by phosphonylation with diethyl chlorophosphite and then oxidation with hydrogen peroxide. This protocol provided the desired phosphonates with satisfactory yields. This procedure also had some limitations in its dependence on the accessibility and stability of the lithiated heterocyclic compounds. The same procedure could be applied to phosphonylation of aromatic compounds, which do not undergo direct lithiation and thus require the use of their bromides as substrates. The obtained compounds showed weak antiproliferative activity when tested on three cancer cell lines.

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Regioselective Synthesis of α- and γ-Amino Quinolinyl Phosphonamides Using N-Heterocyclic Phosphines (NHPs)

Cited by 10 publications

References 46 publications

Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

One-Pot Phosphonylation of Heteroaromatic Lithium Reagents: The Scope and Limitations of Its Use for the Synthesis of Heteroaromatic Phosphonates

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