Facile one-pot synthesis of functionalized organophosphonate esters via ketone insertion into bulky arylphosphites (original) (raw)

Recent Advances in H-Phosphonate Chemistry. Part 1. H-Phosphonate Esters: Synthesis and Basic Reactions

Topics in Current Chemistry, 2014

This review covers recent progress in the preparation of H-phosphonate mono-and diesters, basic studies on mechanistic and stereochemical aspects of this class of phosphorus compounds, and their fundamental chemistry in terms of transformation of P-H bonds into P-heteroatom bonds. Selected recent applications of H-phosphonate derivatives in basic organic phosphorus chemistry and in the synthesis of biologically important phosphorus compounds are also discussed.

Synthesis of new phosphonato esters by reaction between triphenyl or trialkyl phosphite and acetylenic diesters in the presence of NH-containing compounds

Heteroatom Chemistry, 2011

The reaction between triphenyl or trialkyl phosphite and acetylenic esters in the presence of some heterocyclic or aromatic NH compounds such as thiazolidine-2,4-dione, 2-methyl indole, 5-bromoisatine, 3-nitroacetanilide, saccharin, 5,5-dimethylhydantoin, 2-nitroaniline, 4-nitroaniline, benzophenon hydrazine, and anthranilic acid led to the formation of phosphonato esters in high yield.

Allenylphosphonates with a 1,3,2-dioxaphosphorinane ring: Synthesis, structures, stability and utility

Journal of Chemical Sciences, 2009

Synthesis, structures and stability (thermal and air) of allenylphosphonates of the type (OCH 2 CMe 2 CH 2 O)P(O)C(R)=C=CR′R″ and [R″R′C=C=C(R)P(O)(OCH 2) 2 ] 2 C are discussed. Thermally activated dimerization (cycloaddition) of (OCH 2 CMe 2 CH 2 O)P(O)C(H)=C=CMe 2 leads to the phosphonocyclobutane [(OCH 2 CMe 2 CH 2 O)P(O)C(H)=] 2 [C-CMe 2 ] 2 (18). Many of these allenes undergo addition of diethylamine to lead to enaminophosphonates that are readily hydrolysed by water to lead to βketophosphonates. The latter compounds are useful as Horner-Wadsworth-Emmons (HWE) reagents. Molecular structures of (OCH 2 CMe 2 CH 2 O)P(O)C(CH 2 OH)=C=CH 2 (6), [H 2 C=C=C(H)P(O)(OCH 2) 2 ] 2 C (9), (OCH 2 CMe 2 CH 2 O)P(O)CH=C=CH 2 (12), [(OCH 2 CMe 2 CH 2 O)P(O)C(H)=] 2 [C-CMe 2 ] 2 (18), and the β-ketophosphonate (OCH 2 CMe 2 CH 2 O)P(O)CH 2)-C(O)CHMe 2 (24) have been determined. In compound 6, intermolecular hydrogen bonding between the phosphoryl oxygen and the hydroxyl group leading to an infinite chain is observed. In 6, there is a significant deviation (ca 7°) from the orthogonality expected between the planes containing 4 atoms of (a) H 2 C=C and (b) C=C(H)P in the allene part. In 9, weak C-H…O interaction between the phosphoryl oxygen atom and a CH 2 proton of the six-membered ring is present.

Synthesis and Characterization of Novel Alkyl-Substituted Aryl Diphenylphosphinate Esters

Phosphorus Sulfur and Silicon and The Related Elements, 2011

In this work, the reactions of diphenylphosphinic chloride, (C 6 H 5) 2 P(O)Cl, 1, with the sodium salts of sterically hindered phenol derivatives (2a-2j) were investigated. Novel alkyl-substituted aryl diphenyl phosphinate esters (C 6 H 5) 2 P(O)OAr (3-12) were obtained from these reactions. Satisfactory analytical and spectroscopic results were obtained for all the new compounds.

To date the greenest method for the preparation of α-hydroxyphosphonates from substituted benzaldehydes and dialkyl phosphites

Green Processing and Synthesis, 2017

Recent synthetic methods for α-hydroxyphosphonates comprise a green, solvent-free accomplishment of the Pudovik reaction that was typically followed by extractions and recrystallization, or even by chromatography, or other operations. We now developed a general procedure applying 10% of triethylamine as the catalyst and a minimum quantity of acetone as the solvent, giving the products in a pure form after a reflux of 5–120 min following the addition of some n-pentane and crystallization on cooling.