Synthesis Of Β-ketophosphonates Research Articles

New β-ketophosphonates for the synthesis of prostaglandin analogues. 1. Phosphonates with a bicyclo[3.3.0]octene scaffold spaced by a methylene group from the β-ketone

The synthesis of β-ketophosphonates, linked by a methylene group to a bicyclo[3.3.0]octene fragment, was performed by the reaction of dimethyl methanephosphonate with the ester group of two intermediates with this scaffold. Starting from a diol, protected with good leaving groups (mesyl and tosyl), we performed a sequence of reactions with good yields: the carbon chain lengthening by reaction with KCN, the hydrolysis of the nitrile groups to carboxyl, the esterification of carboxyl to ester and finally the phosphonate synthesis, which gave one bis-β-ketophosphonate and two mono β-ketophosphonates. The new β-ketophosphonates are key intermediates for obtaining new prostaglandin analogues with a bicyclo[3.3.0]octene fragment in the ω-side chain. The bicyclo[3.3.0]octane scaffold, found in natural products and in anticancer compounds, are expected to keep their activity in PG analogs; the bulky scaffold, separated by a methylene group from the C-15 carbon atom, is expected to diminish the inactivation of the PG analog by enzyme oxidation of 15α-OH oxidation to 15-Keto via PGDH pathway.

ChemInform Abstract: Chemoselective Synthesis of β‐Ketophosphonates Using Lithiated α‐(Trimethylsilyl)methylphosphonate.

AbstractDimethyl methylphosphonate as reactant gives lower yields.

Synthesis of β-ketophosphonates via AgNO3-catalyzed hydration of alkynylphosphonates: a rate-enhancement effect of methanol

β-Ketophosphonates were prepared via AgNO3-catalyzed hydration of alkynylphosphonates with a dramatic rate-enhancement effect of methanol. This benign aqueous-methanol method catalyzed by a low-cost catalyst has simple, atom-economical procedure, and was used effectively with a wide range of substrates.

ChemInform Abstract: Acylation of Diethyl Phosphonoacetic Acid via the MgCl2/Et3N System: A Practical Synthesis of β-Keto Phosphonates.

Abstract 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.

Synthesis of β-ketophosphonates with electron rich β-aryl groups as useful organophosphorus reagents in lignans synthesis

Investigation of the oxidation reaction of electron rich alkoxy substituted β-aryl β-hydroxyphosphonates to corresponding β-ketophosphonates, which may be utilized in syntheses of lignans with various oxidizing agents (PCC, PDC, SIBX, CAN, Oxone ®, KMNO 4/SiO 2, KMnO 4/MS 4 Å, KMnO 4/CuSO 4, KMnO 4/CuSO 4/Al 2O 3, MnO 2, CrO 3/SiO 2, H 2O 2/salen) is described. The effect of oxidants and reaction conditions on the reaction efficiency and yield was also investigated.

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.

Solid Phase Acylation of Phosphonoacetates Synthesis of β-Keto Phosphonates from Polymer Bound Phosphonoacetate

Solid phase synthesis of phase synthesis of β-keto phosphonates, via acylation reaction of polymer bound phosphoacetate with carboxylic acid chlorides in the presence of magnesium chloride-triethylamine followed by cleavage of resin with concomitant decarboxylation, is described.

New synthesis of β-keto phosphonates

A new synthetic route to β-keto phosphonates from diethyl 1-(trimethylsilyl)vinyl-phosphonate 1 is described. This involves nucleophilic addition of the organolithium reagents toward 1 followed by quenching with acid chlorides and alkyl isocyanates.

The 1,3-migration of phosphorus from oxygen to carbon: A new synthesis of β-ketophosphonates from enol phosphates

Enol phosphates, readily prepared from ketone enolates and dialkyl phosphorochloridate, can be converted to the analogous β-ketophosphonates by treatment with strong base.