1034-94-2

We report here an unprecedented Fe/Cu synergistically catalyzed deesterificative or deamidative oxyphosphorylation of unsaturated carboxylates or amides with H-phosphonates. The valuable β-ketophosphonates were obtained along with chemoselective cleavage of Csp2-C(CO) or Csp-C(CO) bonds in good yields under oxygen atmosphere with a wide substrate scope.

A copper/iron-catalyzed oxyphosphorylation of alkynes with H-phosphonates through a radical process was developed. The present protocol provides an attractive approach to β-ketophosphonates in moderate to good yields, with the advantages of readily available substrate, high functional group tolerance and operation simplicity. (Chemical Equation Presented).

An effective and facile transitio-metal-free method has been developed for the synthesis of β-ketophosphine oxides from alkynylphosphine oxides with benzaldehyde oxime as a hydroxide surrogate. The current methodology provides simple access to various β-ketophosphine oxides in moderate to excellent yields with a broad substrate scope.

An efficient and mild route for the formation sulfur or phosphor-substituted alkynes was herein demonstrated. The Mukaiyama reagent-mediated transformation started from easily-accessible substrates without carbon-carbon triple bonds, and the reaction proceeded under mild conditions (room temperature) in a one-pot manner, requiring for no transition metal-catalysts. The practical protocol featured for good functional groups tolerance (up to 41 examples) and high efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.

A simple and convenient copper-catalyzed direct oxyphosphorylation of enamides with P(O)-H compounds and dioxygen has been developed under mild conditions. This methodology can allow the synthesis of a series of valuable β-ketophosphine oxides/β-ketophosphonates in moderate to good yields with a broad substrate scope simply by using readily-available starting materials.

The invention discloses a method for synthesizing beta-carboxyl phosphate from alkyne or alkynyl carboxylic compounds and phosphite ester in the presence of copper/iron salt serving as catalysts and molecular oxygen serving as an oxidant. According to the method, multifunctional beta-carboxyl phosphate is obtained by virtue of a novel method having wide substrate range in the presence of the inexpensive catalysts (copper salts and iron salts) in oxygen, which is in a sharp contrast with previously reported view that alkyne cannot act in the presence of molecular oxygen. The method disclosed by the invention has the advantages of mild reaction conditions, easily available raw materials, good compatibility with various reactants, strong practicality and high yield and can be widely applied to various functional reactions.

Cu(i)/Fe(iii)-Catalyzed phosphorylation and oxyphosphorylation of styrenes with H-phosphonates which can be controlled by varying the reaction temperature are developed. This study offers a new and expedient strategy for the synthesis of useful alkenylphosphine oxides and β-ketophosphonates in satisfactory yields. Moreover, the transformation is proposed to proceed via a radical process and exhibits a broad substrate scope and good functional group tolerance.

An unprecedented substituent-controlled chemoselective cleavage of C = C double bond or C(sp2)-C(CO) bond along with aerobic phosphorylation of α,β-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to β-ketophosphonates under mild conditions with a wide substrate scope.

The present invention discloses a preparation method for preparing beta-Ketophosphonates represented by a formula (III). The beta-Ketophosphonate is an oxygen-containing compound having a value, and is especially adopted as an important synthesis intermediate to be widely used in the famous HWE reaction to synthesize alpha,beta-unsaturated carbonyl compounds. According to the present invention, simple and commercialized olefin and hydrogen-phosphorite are adopted as raw materials to directly utilize oxygen as an oxidizing agent and an oxygen source under transition metal catalysis to prepare the beta-Ketophosphonates; the preparation method has advantages of cheap and easily available raw materials, mild reaction conditions, environmental-friendliness, high atom economy, wide substrate adaptability range, and no requirement of harsh reaction conditions such as equivalent organic metal reagent use, low temperature, no water, no oxygen and the like; and the method further has advantages of short preparation period, easy product purification, stable process conditions, convenient operation and safety, and is suitable for large-scale production.

A new synthetic method of trifluoromethylated phosphonates was developed via electrophilic trifluoromethylation with Togni reagent. A variety of β-keto phosphonates were converted into the corresponding α-trifluoromethyl-β-keto phosphonates in moderate to good yields. This protocol could also be extended to other fluoroalkylation reactions, such as pentafluoroethylation.

An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds under mild conditions (0 or -20 °C) in a one-pot manner, and does not require transition-metal catalysts. The base-induced protocol exhibits good functional group tolerance (up to 44 examples) and high efficiency (up to 94 % yield) towards rare heteroatom-substituted acetylenes (N or P). Furthermore, the proposed mechanism was supported by the isolation of a key intermediate. An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds in the absence of any transition-metal catalysts under mild conditions (0 or -20 °C) in a one-pot manner with good functional group compatibility and with high efficiency.

Copper nanoparticles (CuNPs) supported on ZnO have been shown to effectively catalyze the direct synthesis of β-ketophosphonates from alkenes or alkynes, and that of vinyl phosphonates from alkynes and diethylphosphite, under air and in the absence of any additive or ligand. When using alkynes as starting materials, the selectivity proved to be dependent on the nature of the alkyne. Thus, alkynes conjugated with an aromatic ring or a carbon-carbon double bond gave β-ketophosphonates as the main reaction products, whereas aliphatic alkynes or alkynes conjugated with a carbonyl group led to the formation of the corresponding vinyl phosphonates.

A domino Knoevenagel-decarboxylation-alkene difunctionalization sequence has been developed for the conversion of benzaldehydes into β-ketophosphonates, catalyzed by a cooperative Cu/Fe system, whereby CP and CO bonds are formed simultaneously in a one-pot reaction. The reaction proceeds in good yields and with a broad substrate scope and environmentally benign conditions.

A synergistic Cu/Fe-catalyzed aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonate is disclosed. The useful β-ketophosphonate products were obtained in good yields under oxygen atmosphere in a novel way. This reaction exhibits a wide substrate scope, and the mechanistic experiments indicate that a radical mechanism forms both C-P and C=O bonds simultaneously. This mechanism contrasts existing aerobic difunctionalization of alkynes.

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.

A general, efficient, and highly regioselective protocol with the use of a gold(I) complex catalytic system for the transformation of alkynylphosphonates into the corresponding β-ketophosphonates has been successfully developed. This method produces a variety of β-ketophosphonates with the advantages of mild reaction conditions, high functional-group tolerance, and excellent yields. An efficient and mild gold-catalyzed hydration process for the regioselective synthesis of β-ketophosphonates directly from alkynylphosphonates is described. Twenty-two examples with yields of 85-97 % are reported. Different substituents including substituted aryl, alkyl, chloro, ester, sulfonoxyl, and phthalimide groups are tolerated; XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, Tf = trifluoromethylsulfonyl. Copyright

A highly efficient palladium(II)-catalyzed hydration of a wide range of alkynylphosphonates to the corresponding β-ketophosphonates has been developed to give high yields at 80 °C in 1, 4-dioxane, with no acidic or alkaline cocatalysts required. The described catalytic system should provide an efficient alternative to highly toxic mercury-catalyzed methodologies and be useful in synthetic programs. Copyright

Direct access: The title reaction has been developed under mild reaction conditions (see scheme; DMSO=dimethyl sulfoxide). This reaction can be effectively scaled up and offers not only a green and attractive approach to β-ketophosphonates, but also a useful example of direct incorporation of an oxygen atom from dioxygen into organic frameworks. Copyright

The copper-cobalt-nickel separation being an nowadays industrial problem, this work was aimed to correlate the structure of some β carbonyl phosphonate compounds with the extractibility of three corresponding cations (4).The generalised formula of these compounds is: (RO)2P(O)-CH2-C(O)-R' and the way to synthesise them depends upon the nature of R and R' (R is always a saturated hydrocarbon radical).The different samples are described in table I.Toluen has been chosen as the dilutant and the studied pH domain extends from the pH of first contact between phases to the pH of precipitation of the metal hydroxides.The following compounds exhibit a slight affinity for copper, cobalt and nickel: E1 : R' is the phenyl radical.E2, E3 : R' is the parafluorophenyl radical.E5 : R' is a saturated hydrocarbon radical.E9 : R' is a partially fluorine substituted aliphatic radical.The compounds are not interesting for solving the industrial problem with which we are concerned.On the contrary, the following compounds exhibit, in certain conditions (pH, concentration) an excellent affinity for one or another of the three metals, allowing sometimes a complete extraction : E4 (figure 1) : R' is the hydrogen atom.E6, E7, E8 (table II, figure 2 and table III) : R' is a completely fluorine substituted aliphatic radical, by way of example E6 extracts well nickel or cobalt and E7, E8 extract well copper.One can notice the formation of a third phase with E7 (R = -C2H5).The substitution of the ethyl group by the normal butyl (E8, R = -C4H9) increases the lipophilicity of the complex metal phosphonate and the compound E8 is able to realise the purification of diluted cobalt or nickel aqueous solutions towards copper.