Mechanism in organophosphorus chemistry. II. Reaction of trialkyl phosphite esters with N-methylol carboxamides and sulfonamides. Trapping of an intermediate

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.

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Synthesis of α-Aminophosphonates and Related Derivatives; The Last Decade of the Kabachnik–Fields Reaction

Molecules ◽

10.3390/molecules26092511 ◽

2021 ◽

Vol 26 (9) ◽

pp. 2511

Author(s):

Petra R. Varga ◽

György Keglevich

Keyword(s):

Biological Activity ◽

Solvent Free ◽

Trialkyl Phosphite ◽

Catalyst Free ◽

Potential Biological Activity

The Kabachnik–Fields reaction, comprising the condensation of an amine, oxo compound and a P-reagent (generally a >P(O)H species or trialkyl phosphite), still attracts interest due to the challenging synthetic procedures and the potential biological activity of the resulting α-aminophosphonic derivatives. Following the success of the first part (Molecules 2012, 17, 12821), here we summarize the synthetic developments in this field accumulated in the last decade. The procedures compiled include catalytic accomplishments as well as catalyst-free and/or solvent-free “greener” protocols. The products embrace α-aminophosphonates, α-aminophosphinates, and α-aminophosphine oxides along with different bis derivatives from the double phospha-Mannich approach. The newer developments of the aza-Pudovik reactions are also included.

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The role of organonickel reagents in organophosphorus chemistry

Coordination Chemistry Reviews ◽

10.1016/j.ccr.2021.213889 ◽

2021 ◽

Vol 438 ◽

pp. 213889

Author(s):

Zufar N. Gafurov ◽

Alexey A. Kagilev ◽

Artyom O. Kantyukov ◽

Oleg G. Sinyashin ◽

Dmitry G. Yakhvarov

Keyword(s):

Organophosphorus Chemistry

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