Environmentally Benign Syntheses of α-Substituted Phosphonates: Preparation of α-Amino- and α-Hydroxyphosphonates in Water, in Ionic Liquids, and under­ Solvent-Free Conditions

Abstract

Due to the interest in α-amino-and α-hydroxyphosphonates and their derivatives, which arises from the important biological activity exhibited by those compounds, the development of efficient protocols for their preparation is of great importance. In the last 10 years however, the chemistry of α-amino and α-hydroxyphosphonates has been witness to an explosion of research activities in the field of application of environmentally benign media. This fact can be partially attributed to the development of the field of green and sustainable chemistry and especially the implementation of green solvents that has a large potential to contribute to more sustainable processes in chemical, pharmaceutical and processing industries. This review provides the reader with an in-depth overview of advances in the synthesis of α-amino-and α-hydroxyphosphonates under eco-friendy conditions compiled into sections with respect to product type and reaction medium.

Synthesis of α-aminophosphonates using solvate ionic liquids

“…[23][24][25][26][27][28][29] The use of ILs as solvents for this reaction have been reported with some excellent results, [30][31][32][33][34] particularly for the pseudo-ionic liquid 5.0 M lithium perchlorate in dithethyl ether (5 M LPDE), or the use of LiClO 4 as an additive to the reaction mixture.…”

Recent Advances in H-Phosphonate Chemistry. Part 2. Synthesis of C-Phosphonate Derivatives

“…Addition of H-phosphonate diesters to a carbonyl group and its derivatives has been known for years as a convenient way to prepare α-functionalized C-phosphonates, especially α-aminophosphonates and α-hydroxyphosphonates [13,14]. Because of a wide range of practical applications [5][6][7][8], recent research in this area has been focused on finding new catalysts and developing stereoselective approaches [23].…”

“…For the formation of the P-C(sp 3 ) bond, the most common approaches are still those involving the Michaelis-Arbuzov [9,10] and the Michaelis-Becker reactions [11,12], or the addition to a carbonyl group [13,14]. However, in recent decades, the transition metal mediated P-C bond formation strategy has started to become widely used, especially in the synthesis of P-C(sp 2 ) derivatives [5,[15][16][17][18].…”

Methods for synthesis of N-heterocyclyl/heteroaryl- α-aminophosphonates and α-(azaheterocyclyl)phosphonates

“…11 At present, the literature concerning the synthesis and application of α-aminophosphonates is very extensive, comprising more than six thousand publications. Hence, several review articles have been developed for the synthesis of α-aminophosphonic acid and their esters [12][13][14][15][16][17][18] and azaheterocyclic phosphonates. 19 The Pudovik 20,21 and Kabachnik-Fields 22,23 reactions are the main pathways for construction of α-aminophosphonates.…”