An efficient and expedient protocol for the synthesis of benzyl phosphonates using KI/K2CO3 as a catalytic system and PEG-400 as benign solvent has been developed. The reaction proceeds smoothly at room temperature achieving excellent selectivity and yield of the corresponding products. The combination of PEG-400, KI, and K2CO3 in this reaction avoids the need of volatile/toxic organic solvents and reactive alkali metals or metal nanoparticles/hydrides. We believe that this benign combination (PEG-400 and KI) could be used for other related organic transformations.

Department of Chemical Engineering Motilal Nehru National Institute of Technology Allahabad India

Department of Chemistry B N Bandodkar College of Science Mumbai India

Department of Chemistry Institute of Chemical Technology Mumbai India

Department of Chemistry SIES College of Arts Science and Commerce Mumbai India

Department of Physical Chemistry Faculty of Science Regional Centre of Advanced Technologies and Materials Palacky University Olomouc Czech Republic

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Anderson P. M., Wiseman G. A., Dispenzieri A., Arndt C. A. S., Hartmann L. C., Smithson W. A., et al. (2002). High-dose samarium-153 ethylene diamine tetramethylene phosphonate: low toxicity of skeletal irradiation in patients with osteosarcoma and bone metastases. J. Clin. Oncol. 20, 189–196. 10.1200/JCO.20.1.189 PubMed DOI

Anna D., Artur M. (2015). Catalytic and MW-assisted michaelis-arbuzov reactions. Curr. Green Chem. 2, 223–236. 10.2174/2213346102666150128195001 DOI

Bhattacharya A. K., Thyagarajan G. (1981). Michaelis-Arbuzov rearrangement. Chem. Rev. 81, 415–430. 10.1021/cr00044a004 DOI

Bloomfield A. J., Herzon S. B. (2012). Room temperature, palladium-mediated P–arylation of secondary phosphine oxides. Org. Lett. 14, 4370–4373. 10.1021/ol301831k PubMed DOI

Chandrasekhar S., Narsihmulu Ch., Sultana S. S., Reddy N. R. (2003). Osmium tetroxide in poly(ethylene glycol) (PEG): a recyclable reaction medium for rapid asymmetric dihydroxylation under Sharpless conditions. Chem. Commun. 1716–1717. 10.1039/b305154B DOI

Chen J., Spear S. K., Huddleston J. G., Rogers R. D. (2005). Polyethylene glycol and solutions of polyethylene glycol as green reaction media. Green Chem. 7, 64–82. 10.1039/b413546f DOI

Dickerson T. J., Reed N. N., Janda K. D. (2002). Soluble polymers as scaffolds for recoverable catalysts and reagents. Chem. Rev. 102, 3325–3344. 10.1021/cr010335e PubMed DOI

Engel R. (1977). Phosphonates as analogues of natural phosphates. Chem. Rev. 77, 349–367. 10.1021/cr60307a003 DOI

Engel R. (1992). Handbook of Organophosphorus Chemistry. New York, NY: Marcel Dekker.

Fredriksen K. A., Amedjkouh M. (2016). Investigation of reactive intermediates and reaction pathways in the coupling agent mediated phos-phonamidation reaction. Eur. J. Org. Chem. 2016, 474–482. 10.1002/ejoc.201501244 DOI

Gawande M. B., Bonifácio V. D. B., Luque R., Branco P. S., Varma R. S. (2013a). Benign by design: catalyst-free in-water, on-water green chemical methodologies in organic synthesis. Chem. Soc. Rev. 42, 5522–5551. 10.1039/c3cs60025d PubMed DOI

Gawande M. B., Bonifácio V. D. B., Luque R., Branco P. S., Varma R. S. (2014a). Solvent-free and catalysts-free chemistry: a benign pathway to sustainability. ChemSusChem. 7, 24–44. 10.1002/cssc.201300485 PubMed DOI

Gawande M. B., Branco P. S., Varma R. S. (2013b). Nano-magnetite (Fe PubMed DOI

Gawande M. B., Luque R., Zboril R. (2014b). The rise of magnetically recyclable nanocatalysts. ChemCatChem. 6, 3312–3313. 10.1002/cctc.201402663 DOI

Gawande M. B., Rathi A. K., Branco P. S., Varma R. S. (2013c). Sustainable utility of magnetically recyclable nano-catalysts in water: applications in organic synthesis. Appl. Sci. 3, 656–674. 10.3390/app3040656 DOI

Gawande M. B., Rathi A. K., Nogueira I. D., Varma R. S., Branco P. S. (2013d). Magnetite-supported sulfonic acid: a retrievable nanocatalyst for the Ritter reaction and multicomponent reactions. Green Chem. 15, 1895–1899. 10.1039/c3gc40457a DOI

Gawande M. B., Shelke S. N., Zboril R., Varma R. S. (2014c). Microwave-assisted chemistry: synthetic applications for rapid assembly of nanomaterials and organics. Acc. Chem. Res. 47, 1338–1348. 10.1021/ar400309b PubMed DOI

Huang J., Chen R. (2000). An overview of recent advances on the synthesis and biological activity of α-aminophosphonic acid derivatives. Heteroatom Chem. 11, 480–492. 10.1002/1098-1071(2000)11:7<480::AID-HC6>3.0.CO;2-J DOI

Kafarski P., Lejczak B. (1991). Biological activity of aminophosphonic acids. Phosphorus Sulfur Silicon Relat. Elem. 63, 193–215. 10.1080/10426509108029443 DOI

Kale S. R., Kahandal S. S., Burange A. S., Gawande M. B., Jayaram R. V. (2013). A benign synthesis of 2-amino-4H-chromene in aqueous medium using hydrotalcite (HT) as a heterogeneous base catalyst. Catal. Sci. Technol. 3, 2050–2056. 10.1039/c3cy20856g DOI

Kem K. M., Nguyen N. V., Cross D. J. (1981). Phase-transfer-catalyzed michaelis-becker reaction. J. Org. Chem. 46, 5188–5192. 10.1021/jo00338a025 DOI

Kers A., Stawiński J., Dembkowski L., Kraszewski A. (1997). Aryl H-phosphonates. 7. Studies on the formation of phosphorus-carbon bond in the reaction of trityl and benzyl halides with dialkyl and diphenyl H-phosphonates. Tetrahedron 53, 12691–12698. 10.1016/S0040-4020(97)00790-4 DOI

Kittredge J. S., Roberts E. (1969). A carbon-phosphorus bond in nature. Science 164, 37–42. 10.1126/science.164.3875.37 PubMed DOI

Krise J. P., Stella V. J. (1996). Prodrugs of phosphates, phosphonates, and phosphinates. Adv. Drug Delivery Rev. 19, 287–310. 10.1016/0169-409X(95)00111-J DOI

Lavén G., Stawinski J. (2009). Palladium(0)-catalyzed benzylation of H-phosphonate diesters: an efficient entry to benzylphosphonates. Synlett 2009, 225–228. 10.1055/s-0028-1087522 DOI

Manabe K., Kobayashi S. (2000). Facile synthesis of α-amino phosphonates in water using a Lewis acid—surfactant-combined catalyst. Chem. Commun. 669–670. 10.1039/B000319K DOI

Meisters A., Swan J. (1965). Organophosphorus compounds. VI. The ‘abnormal’ Michaelis-Becker reaction. Diethyl 1-phenylepoxyethylphosphonate and diethyl 1-phenylvinylphosphate from diethyl phosphonate and phenacyl chloride. Australian J. Chem. 18, 168–172. 10.1071/CH9650168 DOI

Michalski J., Skowronska A., Łopusinski A. (1991). New chemistry and stereochemistry of organophosphorus pseudohalogens. Phosphorus Sulfur Silicon Relat. Elem. 58, 61–88. 10.1080/10426509108040626 DOI

Quin L. D. (2000). A Guide to Organophosphorus Chemistry. New York, NY: John Wiley & Sons.

Rajeshwaran G. G., Nandakumar M., Sureshbabu R., Mohanakrishnan A. K. (2011). Lewis acid-mediated michaelis−arbuzov reaction at room temperature: a facile preparation of arylmethyl/heteroarylmethyl phosphonates. Org. Lett. 13, 1270–1273. 10.1021/ol1029436 PubMed DOI

Rushing S. D., Hammer R. P. (2001). Synthesis of phosphonamide and thiophosphonamide dipeptides. J. Am. Chem. Soc. 123, 4861–4862. 10.1021/ja015632f PubMed DOI

Saady M., Lebeau L., Mioskowski C. (1995a). Synthesis of di- and triphosphate ester analogs via a modified Michaelis-Arbuzov reaction. Tetrahedron Lett. 36, 5183–5186. 10.1016/00404-0399(50)10097- DOI

Saady M., Lebeau L., Mioskowski C. (1995b). First Use of Benzyl Phosphites in the Michaelis-Arbuzov Reaction synthesis of mono-, Di-, and triphosphate analogs. Helvetica Chim. Acta 78, 670–678. 10.1002/hlca.19950780314 DOI

Sharma R. K., Sharma S., Dutta S., Zboril R., Gawande M. B. (2015). Silica-nanosphere-based organic-inorganic hybrid nanomaterials: synthesis, functionalization and applications in catalysis. Green Chem. 17, 3207–3230. 10.1039/C5GC00381D DOI

Shi D.-Q., Wang Y.-M., Chen R.-Y. (2000). Synthesis and stereoselectivity of a new type of unsaturated phosphonates. Heteroatom Chem. 11, 261–266. 10.1002/1098-1071(2000)11:4<261::AID-HC3>3.0.CO;2-1 DOI

Takahashi H., Inagaki S., Yoshii N., Gao F., Nishihara Y., Takagi K. (2009). Rh-catalyzed negishi alkyl-aryl cross-coupling leading to α- or β-phosphoryl-substituted alkylarenes. J. Org. Chem. 74, 2794–2797. 10.1021/jo900142b PubMed DOI

Timko J. M., Moore S. S., Walba D. M., Hiberty P. C., Cram D. J. (1977). Host-guest complexation. 2. Structural units that control association constants between polyethers and tert-butylammonium salts. J. Am. Chem. Soc. 99, 4207–4219. 10.1021/ja00455a001 DOI

Tomilov A. P., Martynov B. I., Pavlova N. A. (2001). Electrochemical alkylation of diethylphosphite. J. Electroanal. Chem. 507, 46–48. 10.1016/S0022-0728(01)00370-9 DOI

Wang T., Sang S., Liu L., Qiao H., Gao Y., Zhao Y. (2014). Experimental and theoretical study on palladium-catalyzed C–P bond formation via direct coupling of triarylbismuths with P(O)–H compounds. J. Org. Chem. 79, 608–617. 10.1021/jo402392t PubMed DOI

Witt D., Rachon J. (1996). The direct preparation of the esters of p-nitrobenzylphosphonic acid from p-nitrobenzyl halides. Heteroatom Chem. 7, 359–364.

Xu J., Zhang P., Gao Y., Chen Y., Tang G., Zhao Y. (2013). Copper-catalyzed P-arylation via direct coupling of diaryliodonium salts with phosphorus nucleophiles at room temperature. J. Org. Chem. 78, 8176–8183. 10.1021/jo4012199 PubMed DOI