Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates

Huang, Hai; Denne, Johanna; Yang, Chou‐Hsun; Wang, Haobin; Kang, Jun Yong

doi:10.1002/ange.201802082

Cited by 17 publications

(8 citation statements)

References 66 publications

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“…Yield 74%; NMR data in accordance with the literature [ 57 ]; colorless liquid. 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.54–7.46 (m, 1H), 7.47–7.37 (m, 1H), 7.33–7.18 (m, 2H), 3.96 (dq, J H-P = 8.3 Hz, J H-H = 7.0 Hz, 4H), 3.30 (d, J H-P = 10.3 Hz, 2H), 1.17 (t, J H-H = 7.1 Hz, 6H); 13 C NMR (101 MHz, DMSO-d 6 ) δ 135.2 (d, J C-P = 9.0 Hz), 132.4 (d, J C-P = 6.5 Hz), 130.3 (d, J C-P = 2.8 Hz), 129.3 (d, J C-P = 3.4 Hz), 128.8 (d, J C-P = 6.5 Hz), 121.3 (d, J C-P = 3.4 Hz), 61.4 (d, J C-P = 6.4 Hz), 31.6 (d, J C-P = 134.8 Hz), 16.1 (d, J C-P = 5.8 Hz); 31 P NMR (162 MHz, DMSO-d 6 ) δ 25.9.…”

Section: Methodssupporting

confidence: 73%

Selective Esterification of Phosphonic Acids

et al. 2021

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Here, we report straightforward and selective synthetic procedures for mono- and diesterification of phosphonic acids. A series of alkoxy group donors were studied and triethyl orthoacetate was found to be the best reagent as well as a solvent for the performed transformations. An important temperature effect on the reaction course was discovered. Depending on the reaction temperature, mono- or diethyl esters of phosphonic acid were obtained exclusively with decent yields. The substrate scope of the proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small- and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30 °C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic acid). At higher temperatures, similar intermediate forms give diesters or stable and detectable pyrophosphonates which were also consumed to give diesters. 31P NMR spectroscopy was used to assign the structure of pyrophosphonate as well as to monitor the reaction course. No need for additional reagents and good accessibility and straightforward purification are the important aspects of the developed protocols.

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Section: Methodssupporting

confidence: 73%

Selective Esterification of Phosphonic Acids

et al. 2021

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“…Additional mechanistic investigation andf urther applicationo f phosphenium cations in organic synthetic chemistry are ongoing in our laboratory. [18]…”

mentioning

confidence: 99%

Phosphenium‐Cation‐Mediated Formal Cycloaddition Approach to Benzophospholes

Nishimura

Unoh

Hirano

et al. 2018

Chemistry A European J

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A phosphenium-cation-mediated formal [3+2]-cycloaddition reaction of internal alkynes is reported. The reaction proceeds under metal-free conditions to give the corresponding C-P rearranged benzophospholes regioselectively, even when ortho- and para-substituted arylphosphine oxides are starting substrates. Mechanistic studies by P{ H} NMR analysis suggest an involvement of three-membered phosphirenium cation species and C-P rearrangement prior to a ring closure for benzophosphole skeleton formation.

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“…However, a recent report used a Cu(I) catalyst with diaryliodonium salts to perform a direct aryloxylation resulting in a one-step transformation of the diethylphosphonate to the mixed alkyl aryl phosphonate (Fan ˜ana ´s-Mastral and Feringa, 2014). Similarly, triflic anhydride and pyridine can also be used to activate the phosphonate and enable direct aryloxylation (Huang et al, 2018) (Figure 2B). These advances should enable large libraries of mixed alkyl aryl phosphonates to be synthesized and therefore this scaffold may be used not only for broad-spectrum labeling of serine hydrolases but also for selective inhibition of individual serine hydrolase targets.…”

Section: Abpp and Serine Hydrolasesmentioning

confidence: 99%

Strategies for Tuning the Selectivity of Chemical Probes that Target Serine Hydrolases

Faucher

Bennett

Bogyo

et al. 2020

Cell Chemical Biology

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Serine hydrolases comprise a large family of enzymes that have diverse roles in key cellular processes, such as lipid metabolism, cell signaling, and regulation of post-translation modifications of proteins. They are also therapeutic targets for multiple human pathologies, including viral infection, diabetes, hypertension, and Alzheimer disease; however, few have well-defined substrates and biological functions. Activity-based probes (ABPs) have been used as effective tools to both profile activity and screen for selective inhibitors of serine hydrolases. One broad-spectrum ABP containing a fluorophosphonate electrophile has been used extensively to advance our understanding of diverse serine hydrolases. Due to the success of this single reagent, several robust chemistries have been developed to further diversify and tune the selectivity of ABPs used to target serine hydrolases. In this review, we highlight approaches to identify selective serine hydrolase ABPs and suggest new synthetic methodologies that could be applied to further advance probe development. ll

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Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates

Cited by 17 publications

References 66 publications

Selective Esterification of Phosphonic Acids

Selective Esterification of Phosphonic Acids

Phosphenium‐Cation‐Mediated Formal Cycloaddition Approach to Benzophospholes

Strategies for Tuning the Selectivity of Chemical Probes that Target Serine Hydrolases

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