The Kabachnik–Fields reaction: synthetic potential and the problem of the mechanism

Abstract

The published data of the last decade concerning the mechanism of the Kabachnik ± Fields reaction and its significance for the chemistry of organophosphorus compounds as a method for the synthesis of a-amino phosphonates and their numerous functionally substituted derivatives and analogues, such as phosphinates and phosphine oxides, are generalised and systematised. The review discusses the classical version of the Kabachnik ± Fields reaction, its modifications with the use of phosphorus chlorides, neutral esters and inorganic phosphorus acids, as well as chemical processes simulating separate steps of the reaction, viz., hydrophosphorylation of imines and amination of a-hydroxy phosphonates. Data on the practical application of a-amino phosphonates are presented. The bibliography includes 253 references.

Catalytic Kabachnik-Fields reaction: new horizons for old reaction

“…One of possible complications of the Kabachnik-Fields reaction is also obvious: the dialkyl phosphites are able to undergo Abramov addition to C=O bond, giving α-hydroxyphosphonates 5 (Scheme 2, path B). 5,7,9,11 Thus, in the case of three-component process one is faced with competitive addition of either N-H or P-H fragments to C=O bond. This dichotomy was mentioned and discussed in terms of hard (N-H) and soft (P-H) bases.…”

“…However, the most remarkable pathway to the synthesis of α-aminophosphonates is the 6,7 which is a one-pot, three-component procedure using carbonyl compound, amine and dialkyl phosphite (Scheme 2). …”

“…This reaction has been studied in detail and thoroughly reviewed. 7,11 Here we present only essential summary of important characteristics of this reaction.…”

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

“…Possibly the simplest experimental proposal to prepare optically active α-amino-C-phosphinates is the "one-pot" three-component reaction, where the reactants are placed all together with or without solvent and catalyst, which is identical to the Kabachnik-Fields reaction widely studied in the synthesis of α-aminophosphonates [50][51][52].…”

Synthetic methods of cyclic α-aminophosphonic acids and their esters

“…Various synthetic methods for α-aminophosphonic acids and α-aminophosphonates have been reported [14][15][16][17][18][19][20][21][22] and the most straightforward one is the addition of compounds containing a P−H bond to the C=N bond of imines (the Pudovik reaction) (Scheme 1). 23 However, the most useful pathway to the synthesis of α-aminophosphonates is the Kabachnik-Fields reaction, [24][25][26][27] which is a one-pot, three-component procedure using carbonyl compound, amine and dialkyl phosphite (Scheme 2). This process was discovered at a time when multicomponent processes were rather "exotic birds"; from a modern point of view this protocol is obviously very attractive for combinatorial chemistry and has been rarely used for parallel synthesis.…”