A Simple Heterogeneous Catalyst for Phosphite Addition on Carbonyl Groups

Abstract

A cheap and easily recoverable heterogeneous catalyst could efficiently trigger C-P bond formation by selective addition of phosphites to the carbonyl group of aldehydes and ketones. The reactions afford the desired products in good to excellent yields and do not require the presence of a solvent.

Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis

“…So far, catalysts activating the carbonyl are quite rarely presented in the literature and heteropolyacids of structure H 6 P 2 W 18 O 62 ·14H 2 O [ 28 ], CeCl 3 ·7H 2 O [ 29 ], or ammonium metavanadate (NH4VO3) are worth mentioning [ 30 ]. More commonly described in the literature are catalysts activating the P-nucleophiles, and for this the cyclopentadienyl ruthenium(II) complex ([RuClCp(PPh 3 ) 2 ] [ 31 ], hydrotalcite MG7 [ 32 ], n -BuLi [ 33 ], amidate ytterbium amide {Yb[N(SiMe 3 ) 2 ](κ 2 -L 1 ) 2 (THF) (L 1 = C 6 H 5 C(O)NC 6 H 3 ( i Pr) 2 )} [ 34 ], potassium phosphate (K 3 PO 4 ) [ 35 ], 2- tert -butyl-imino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazapho-sphorine supported on polystyrene (PSsBEMP) [ 36 ], methylene-linked pyrrolyl samarium and yttrium amido complexes [ 37 ], or molybdenum dichloride dioxide (MoO 2 Cl 2 ) [ 38 ] are of special importance. Finally, bifunctional catalysts activating both carbonyl and phosphonate substrates are known and here Fe 3 O 4 @SiO 2 -Met-Cu(II) in the presence of tert -butyl hydroperoxide (TBHP) [ 39 ], Bi(NO 3 ) 3 .H 2 O [ 40 ], choline chloride [ 41 ], bimetallic samarium bis(cyclopentadienyl) derivatives supported by bridged bis(guanidinate) ligands {(CH 3 C 5 H 4 ) 2 Sm[( i PrN) 2 CN(CH 2 ) 2 ]} 2 [ 42 ], sodium-modified fluoroapatite (Na@FAP) [ 43 ], nafion resin-supported oxovanadium(IV) catalyst [ 44 ], and sodium-modified-hydroxyapatite (Na-HAP) [ 45 ] should be pointed out.…”

Synthesis ofα‐Hydroxyphosphonates Containing Functionalized 1,2,3‐Triazoles

“…Among the different reactions involving hydrophosphoryl compounds, [19–25] the synthesis of α ‐ and β ‐hydroxyphosphonates by the Abramov and the Pudovik reactions have gained significant attention, because of their mild conditions and high atom‐economy [26–31] . Abramov is a method which involves the reaction between hydrophosphoryl reagent with carbonyl compounds, while Pudovik is related to the nucleophilic attack to an imine organic function.…”