A convenient one-pot two-step synthesis of pyrazolylphosphonates from ethynylphosphonate

Mitrofanov, Alexander Yu.; Beletskaya, I. P.

doi:10.1016/j.mencom.2021.07.033

Cited by 9 publications

(2 citation statements)

References 18 publications

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“…This is, to the best of our knowledge, the first example of PPh 3 synthesis without the involvement of P 4 . There are many established procedures that convert 2b into other useful organophosphorus compounds as well. − Moreover, ethynyl phosphonate offers opportunities for terminal phosphate modification of bioactive molecules. Nucleoside tetraphosphate 4 featuring a “clickable” moiety, for example, can be readily synthesized from the TBA salt 2′ using a diphosphorylation protocol recently developed by our group (Figure B) .…”

Section: Resultsmentioning

confidence: 99%

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Xin

Cummins

2023

ACS Cent. Sci.

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In pursuit of a more sustainable route to phosphorus−carbon (P−C) bond-containing chemicals, we herein report that phosphonates can be prepared by mechanochemical phosphorylation of acetylides using polyphosphates in a single step, redoxneutral process, bypassing white phosphorus (P 4 ) and other high-energy, environmentally hazardous intermediates. Using sodium triphosphate (Na 5 P 3 O 10 ) and acetylides, alkynyl phosphonates 1 can be isolated in yields of up to 32%, while reaction of sodium pyrophosphate (Na 4 P 2 O 7 ) and sodium carbide (Na 2 C 2 ) engendered, in an optimized yield of 63%, ethynyl phosphonate 2, an easily isolable compound that can be readily converted to useful organophosphorus chemicals. Highly condensed phosphates like Graham's salt and bioproduced polyphosphate were also found to be compatible after reducing the chain length by grinding with orthophosphate. These results demonstrate the possibility of accessing organophosphorus chemicals directly from condensed phosphates and may offer an opportunity to move toward a "greener" phosphorus industry.

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Section: Resultsmentioning

confidence: 99%

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Xin

Cummins

2023

ACS Cent. Sci.

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“…Synthesis of diethyl alkynylphosphonates . Diethyl ethynylphosphonate ( 2 ) [12c] and diethyl (3‐hydroxyprop‐1‐yn‐1‐yl)phosphonate ( 4 b ) [13] was prepared according to the literature procedures. Diethyl (3‐hydroxy‐3‐methylbut‐1‐yn‐1‐yl)phosphonate ( 4 a ), diethyl (4,4,4‐trifluoro‐3‐hydroxybut‐1‐yn‐1‐yl)phosphonate ( 4 c) and diethyl (3‐hydroxy‐3‐phenylprop‐1‐yn‐1‐yl)phosphonate ( 4 d ) were prepared according to the same procedure as 4 b [13] …”

Section: Methodsmentioning

confidence: 99%

Base‐promoted Synthesis of Trifluoromethylated (1,3‐dioxolan‐4‐ylidene)methylphosphonates from Trifluoromethylketones and Ethynylphosphonates

2021

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1‐Alkynylphosphorus Compounds in Organic Synthesis, 2010–2024

Ni,

Wen,

Xue

et al. 2024

Adv Synth Catal

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Since the review of Yorimitsu and Oshima in 2010, the past 15 years have witnessed significant progresses in the application of 1‐alkynylphosphorus compounds in organic synthesis. Owing to the reactive carbon‐carbon triple bond in association with the electron‐withdrawing phosphoryl group, they easily undergo transition metal‐catalyzed nucleophilic addition reactions at the β‐position with carbon‐ and heteroatom‐based nucleophiles to afford structurally diverse 1‐alkenyl phosphorus compounds. Especially, when 1‐alkynylphosphonates or phosphinates are used, intramolecular substitution reactions on P‐atom might occur in some cases, which would result in the formation of P‐based heterocycles. In addition, the existing triple bond makes them prone to go through addition reaction initiated cyclization reactions and [2+2], [2+3], [2+4], [2+5] and [2+2+2] cycloaddition reactions with other unsaturated bonds, which provides an efficient access to various P‐based heterocycles and phosphorylated carbon‐ and heterocycles.

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A convenient one-pot two-step synthesis of pyrazolylphosphonates from ethynylphosphonate

Cited by 9 publications

References 18 publications

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Base‐promoted Synthesis of Trifluoromethylated (1,3‐dioxolan‐4‐ylidene)methylphosphonates from Trifluoromethylketones and Ethynylphosphonates

1‐Alkynylphosphorus Compounds in Organic Synthesis, 2010–2024

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