On A Safe and Practical Method for The Preparation of β-Keto Phosphonates1

Acylations of the magnesium enolate derivatives of trimethyl and triethylphosphonoacetates, using a magnesium chloride-triethylamine system, lead to 2-acylphosphonoacetates which are decarbalkoxylated to give β-keto phosphonates.     

Synthesis of α-phosphorylated cyclopentanones by intramolecularcarbenoid cyclizations of α-diazo β-keto alkylphosphonates and phosphine oxides

α-diazo β-ketoalkylphosphonates and phosphine oxides undergo intramolecular carbenoīd cyclizations under rhodium (II) catalysis to afford substituted diethoxyphosphono-2 and diphenylphosphono-2 cyclopentanones which, under Wittig-Horner conditions, lead to α-methylene cyclopentanones.     

Silver-Phosphonate Based Metal Organic Frameworks: Synthesis and Antibacterial Action

Silver based Metal Organic Framework (MOF) materials were synthesized by the reaction of phospho-benzoic acid with silver salts under hydrothermal treatment and with/without urea. According to this procedure, either both functional groups (phosphonic acid and carboxylic acid) were engaged in iono-covalent bonds with silver atoms or, on the contrary, only the phosphonic acid function is engaged. Consequently, these materials exhibited different stability and their ability to release silver salts, when they were placed in water, was different. The antibacterial properties of these materials were attributed to the silver salt, released in solution.     

Towards the syntheses of N‐H and N‐alkylated derivatives of meridianins

Novel N‐H and N‐alkylated derivatives of meridianins have been synthesized as potential antitumor agents by a two‐step conversion of N‐tosyl‐3‐acetylindoles or N‐alkyl‐3‐acetylindoles to the corresponding enaminones using DMF‐DMA, with or without added pyrrolidine. Further cyclization with guanidine gave the corresponding 2‐aminopyrimidines. The structures of the compounds, thus obtained, were proved by ¹H and ¹³C NMR spectroscopy, NOE experiments and X‐ray analysis.     

An unexpected base-induced [1,4]-phospho-Fries rearrangement

An unexpected [1,4]-phospho-Fries rearrangement that gives rise to the formation of a O,O,O,O-tetraethyl methylenebis(thiophosphonate) derivative is reported. The regioselectivity of the metallation with n-BuLi or t-BuLi is the key factor that explains either the [1,4] or [1,3] rearrangement observed.     

Acylation of Diethyl Phosphonoacetic Acid Via the MgCl2/Et3N System: A Practical Synthesis of β-Keto Phosphonates

A one pot simple procedure for the synthesis of β-keto phosphonates has been developed using the MgCl₂/Et₃N base system to generate the magnesium enolate of diethyl phosphonoacetic acid. This intermediate reacts with acid chlorides or imidazolides to give, after workup, the title compounds in good yields.