Abstract

The purpose of this review is to summarize the importance of microwave (MW) irradiation as a kind of catalyst in organophosphorus chemistry. Slow or reluctant reactions, such as the Diels-Alder cycloaddition or an inverse-Wittig type reaction, may be performed efficiently under MW irradiation. The direct esterification of phosphinic and phosphonic acids, which is practically impossible on conventional heating, may be realized under MW conditions. Ionic liquid additives may promote further esterifications. The opposite reaction, the hydrolysis of P-esters, has also relevance among the MW-assisted transformations. A typical case is when the catalysts are substituted by MWs, which is exemplified by the reduction of phosphine oxides, and by the Kabachnik–Fields condensation affording α-aminophosphonic derivatives. Finally, the Hirao P–C coupling reaction may serve as an example, when the catalyst may be simplified under MW conditions. All of the examples discussed fulfill the expectations of green chemistry.

Highlights

  • Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations

  • The spread of the microwave (MW) technique opened a new chapter in organic chemistry in whole [1,2,3], and in its specialized fields, such as heterocyclic [3,4,5] and organophosphorus chemistry [2,6]

  • A widely accepted concept is that the efficiency of the MW irradiation is the consequence of the statistically occurring local overheating in the bulk of the mixture [9,10,11]

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Summary

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Molecules 2021, 26, x FOR PEEMRoRdEeVlIERWepahcotsiopnholane oxides (12 and 14), a[sbwmeilml–a][sP, Fa61]-hydroTx2(y3°-C51,)2,3,4,5,6t-(h3he)xahydrYoipehl6do7s(p%2h)oinf 7ine oxide (16) (Table 2) [29,30,31]. Using IL-catalysis, even phenols co–uld be the rea2c2ta0nts in the M4 W-assisted31esterifica-. The esterification of the reactive phenyl-H-phosphinic acid (18) took place at a tem-. The presence of [bmim][PF6] had a beneficial effect on the outcome (Scheme 5/(1)) [34]. Molecules 2021, 26, x FOR PEER REVIaEcWid (22), could be efficiently esterified in the presence of an IL (Scheme 5/(25) oafnd. Table 3(.3M))W[3‐4p,r3o5m].oted direct esterification of phenylphosphonic acid (26)

OBRuct Et
PrBr iPrBr nPrBr
EqEuETqiqvMuuaTiDlivevMSnaaltDleeonSnftt of of
Equivalent of PMHS
Phosphine a a b
PEER PEER
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