The Kabachnik–Fields (phospha-Mannich) reaction involving the condensation of primary or secondary amines, oxo compounds (aldehydes and ketones) and >P(O)H species, especially dialkyl phosphites, represents a good choice for the synthesis of α-aminophosphonates that are of significant importance due to their biological activity. In general, these three-component reactions may take place via an imine or an α-hydroxy-phosphonate intermediate. The monitoring of a few Kabachnik–Fields reactions by in situ Fourier transform IR spectroscopy has indicated the involvement of the imine intermediate that was also justified by theoretical calculations. The Kabachnik–Fields reaction was extended to >P(O)H species, comprising cyclic phosphites, acyclic and cyclic H-phosphinates, as well as secondary phosphine oxides. On the other hand, heterocyclic amines were also used to prepare new α-amino phosphonic, phosphinic and phosphine oxide derivatives. In most cases, the synthesis under solvent-free microwave (MW) conditions is the method of choice. It was proved that, in the cases studied by us, there was no need for the use of any catalyst. Moreover, it can be said that sophisticated and environmentally unfriendly catalysts suggested are completely unnecessary under MW conditions. Finally, the double Kabachnik–Fields reaction has made available bis(phosphonomethyl)amines, bis(phosphinoxidomethyl)amines and related species. The bis(phosphinoxidomethyl)amines serve as precursors for bisphosphines that furnish ring platinum complexes on reaction with dichlorodibenzonitriloplatinum.

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and Economics, in 1996, and he was the head of this Department in the period of 1999-2006. After a fusion in 2007, he has been the head of the Department of Organic Chemistry and Technology. His research interests include organophosphorus and environmentally friendly chemistry comprising P-heterocycles, low-coordinated P-fragments, P(III)-ligands, their borane-and transition metal complexes, catalytic reactions, selective syntheses, resolution of P(IV) compounds, microwave synthesis, ionic liquids, and optimization of reactions by on-line methods. Scheme 8. Synthesis of Pt(II)-(BABAR-Phos) Scheme 9. Synthesis of BABAR-Phos Derivatives Scheme 10. Synthesis of Dibenzo-1-phosphasemibullvalene and Its W-Complex Scheme 11. Synthesis of Phospha[n]triangulanes and Their W-Complexes Scheme 12. Ring-Opening of Phosphiranes

It is well-known that phosphinic acids do not undergo direct esterifications with alcohols under thermal conditions. However, the esterifications take place under microwave (MW) irradiation due to the beneficial effect of MW. As a comparison, maximum 12-15% conversions were observed on traditional heating. It was proved experimentally that the MW-assisted esterifications are not reversible under the conditions applied that may be the consequence of the hydrophobic medium established by the long chain alcohol/phosphinic ester. Neither the thermodynamic, nor the kinetic data obtained by high level quantum chemical calculations justify the direct esterification of phosphinic acids under thermal conditions. The thermodynamic data show that there is no driving force for the reactions under discussion. As a consequence of the relatively high values of activation enthalpy (102-161 kJ mol(-1)), these esterifications are controlled kinetically. Comparing the energetics of the esterification of phosphinic acids and the preparative results obtained under MW conditions, one can see the potential of the MW technique in the synthesis of phosphinates. During our study, a series of new cyclic phosphinates with lipophilic alkyl groups was synthesized.

It was proved by our experiments that on microwave irradiation, the mono‐ or bidentate phosphorus ligands generally applied in the palladium(II)‐catalyzed P–C coupling reaction of aryl bromides and dialkyl phosphites or secondary phosphine oxides may be substituted by the excess of the >P(O)H reagent that exists under a tautomeric equilibrium. Taking into account that the reduction of the palladium(II) salt and the ligation of the palladium(0) so formed requires 3 equivalents of the P‐species for the catalyst applied in a quantity of 5–10%, all together, 15–30% of the P‐reagent is necessary beyond its stoichiometric quantity. In the coupling reaction of diphenylphosphine oxide, it was possible to apply diethyl phosphite as the reducing agent and as the P‐ligand. The reactivities of the diethyl phosphite and diphenylphosphine oxide reagents were compared in a competitive reaction. The mechanism and the energetics of this new variation of the Hirao reaction of bromobenzene with Y2P(O)H reagents (Y=EtO and Ph) was explored by quantum chemical calculations. The first detailed study on simple reaction models justified our assumption that, under the conditions of the reaction, the trivalent form of the >P(O)H reagent may serve as the P‐ligand in the palladium(0) catalyst, and shed light on the fine mechanism of the reaction sequence. The existence of the earlier described bis(palladium complex) {[H(OPh2P)2PdOAc]2} was refuted by high level theoretical calculations. This kind of complex may be formed only with chloride anions instead of the acetate anion. The interaction of palladium acetate and Y2P(O)H may result in only the formation of the [(HO)Y2P]2Pd complex that is the active catalyst in the Hirao reaction. The new variation of the Hirao reaction is of a more general value, and represents the greenest protocol, as there is no need for the usual P‐ligands. Instead, the >P(O)H reagent should be used in an excess of up to 30%. Hence, the costs and environmental burdens may be decreased.

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The general value of the title reaction affording diethyl arylphosphonates, alkyl diphenylphosphinates and tertiary phosphine oxides was demonstrated.

Different types of cyclic phosphine oxides, such as tetrahydrophosphole oxide 1, phosphabicyclo[3.1.0]hexane 3oxide 8 and phosphabicyclo[2.2.1]heptene 7-oxides 10 and 12 were efficiently converted to phosphine-boranes 2, 9, 11 and 13, respectively, under relatively mild conditions by reaction with 4.4 equivalents of dimethyl sulfide-borane. The more strained hetero-ring the starting phosphine oxide (in general 16) has, the easier to accomplish the change in the P-function, that takes place through the corresponding phosphine intermediate ( 20). It is noteworthy that the imide carbonyl groups in starting materials 10 and 12 were fully reduced by the borane to give 11 and 13 respectively.