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Synthesis 2017; 49(14): 3069-3083
DOI: 10.1055/s-0036-1589031
short review
© Georg Thieme Verlag Stuttgart · New York

Advantages of the Microwave Tool in Organophosphorus Syntheses

György Keglevich*
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary   Email: gkeglevich@mail.bme.hu
,
Nóra Zsuzsa Kiss
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary   Email: gkeglevich@mail.bme.hu
,
Alajos Grün
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary   Email: gkeglevich@mail.bme.hu
,
Erika Bálint
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary   Email: gkeglevich@mail.bme.hu
,
Tamara Kovács
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary   Email: gkeglevich@mail.bme.hu
› Author AffiliationsThis project was supported by the Hungarian Research Development and Innovation Fund (K119202).
Further Information

Publication History

Received: 14 March 2017

Accepted after revision: 11 April 2017

Publication Date:
20 June 2017 (online)

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Abstract

The microwave (MW) technique has become an important tool also in the organophosphorus field of organic chemistry. On the one hand, otherwise reluctant reactions, such as the esterification of P-acids, may be enhanced by the effect of MW, while on the other hand, catalysts may be omitted, or catalyst systems may be simplified on MW irradiation. This later group includes the Kabachnik–Fields reactions, alkylation of active methylene-containing compounds, O-alkylations, deoxygenations, as well as the Hirao reaction. It is also the purpose of this review to elucidate the scope and limitations of the MW tool, to interpret the MW effects, and to model the distribution of local overheatings and their beneficial effect.

1 Introduction

2 The Esterification of Phosphinic Acids

2.1 Synthetic Results

2.2 Scope and Limitation of the Application of MWs

2.3 Modelling the Distribution of the Local Overheatings and Predicting­ Their Effect

3 The Simplification of Catalytic Systems

3.1 Replacement of the Catalyst by MW Irradiation

3.1.1 The Kabachnik–Fields Reaction

3.1.2 Solid–Liquid Phase Alkylation of Active Methylene-Containing Compounds

3.1.3 Solid–Liquid Phase Alkylation of Phosphinic Acids

3.1.4 The Deoxygenation of Phosphine Oxides

3.2 The Hirao Reaction without Added P-Ligands

4 Conclusions

Key words

organophosphorus chemistry - microwave irradiation - phosphinates - Kabachnik–Fields reaction - alkylation, deoxygenation - Hirao reaction