Phosphoric acid derivatives, synthesis

Synthesis of glycosyl phosphates by reaction of hemiacetals with activated phosphoric acid derivatives... 

A BINOL-derived phosphoric acid derivative has been used as a catalyst in the enantioselective synthesis of a-amino phosphonates via hydrophosphonylation of imines with diisopropyl phosphite.82... 

The reactions of the betaines I demonstrate the great variety of applications of these compounds for the preparation of substituted phosphoric and thio-phosphoric acid derivatives, and they open new routes for the synthesis of new or difficult to prepare compounds. 

Tatsui G (1928) Synthesis of carboline derivatives. J Pharm Soc Jpn 48 453 159 Taylor MS, Jacobsen EN (2004) Highly enantioselective catalytic acyl-pictet-spengler reactions. J Am Chem Soc 126 10558-10559 Terada M, Uraguchi D, Sorimachi K, Shimizu H (2005) Process for production of optically active amines by stereoselective nucleophilic addition reaction of imines with C nucleophiles using chiral phosphoric acid derivative. PCT Int Appl WO 2005070875 2005-08-04... 

The use of phosphorous acid derivatives in synthesis has been reviewed. ... 

The first, asymmetric, three-component [4 + 2] cycloaddition reaction of cinnamaldehydes (179), primary amines (180), and azalactones (178) by using the phosphoric acid derivative (123) as the catalyst, which yielded 3-amino-3,4-dihydropyridinones (181) in high enantioselectivity (up to 96%), has been disclosed by Gong et al. (Scheme 49). The use of this reaction in the synthesis of benzo[<2]quinolizidine derivatives of high optical purity has been also described. 

In the past year, the development of chemistry of phosphoric acid derivatives has been connected mainly with the topic of synthesis for biological applications. In this section, there will be discussed syntheses of various biological molecules in the form of free phosphoric acids and their salts as well as amide, diester or dithioster derivatives. 

In this chapter, mainly the ROP of cyclic P-containing monomers is discussed. The synthesis of P-containing polymers by the polyaddition is discussed only for the reaction of phosphoric acid derivatives with diepoxides. 

You and coworkers developed a desymmetrization protocol based on an intramolecular oxo-Micliael reaction, using as catalyst the phosphoric acid derivative 121 [110]. Cyclohexadienones 120 were transformed into the corresponding bicyclic systems 122 with high yields and enantioselectivities. Remarkably, the 4-substituent in the cyclohexadienone has a great influence on the enantioselective outcome of the reaction. Bulkier substituents at the 4-position lead to lower reaction rates and enantioselectivities (Scheme 33.35). This desymmetrization reaction was used as a key reaction for the efficient synthesis of the natural products cleroindicins C,... 

A Methylamino)phenol. This derivative (15) is easily soluble ia ethyl acetate, ethanol, diethyl ether, and benzene. It is also soluble ia hot water, but only spatingly soluble ia cold water. Industrial synthesis is by heating 3-(A/-methylamino)benzenesulfonic acid with sodium hydroxide at 200—220°C (179) or by the reaction of resorciaol with methylamiae ia the presence of aqueous phosphoric acid at 200°C (180). 

A further important group of derivatives is that of amino acids activated by phosphoric acid or its esters. In nature, phosphorylation processes play an important activating role in peptide and protein synthesis. 

Thiotraamidophosphoric acids (35) are isoelectronic with phosphoric acids and were initially reported from the reaction of phosphorus pentasulfide with primary amines at high temperatures.62 Subsequently, an improved synthesis for 35 with increased yields and milder conditions has been reported involving the room temperature reaction of thiophosphoryl chloride and primary amines (Equation 50).63 The most convenient route to the analogous selenium derivatives SeP(NHPh)3 is from the oxidation of P(NHPh)3 with elemental selenium (Equation 51).63 Also isoelectronic with phosphoric acids are dithio wamido-phosphoric acids (36), which can be prepared from the reaction of phosphorus pentasulfide with an excess of primary amine at 30°C in toluene (Equation 52).62 The selenium derivatives of 36 can be prepared in a similar reaction from phosphorus (V) selenide, although due to their increased acidity... 

Synthesis of glycosyl phosphates by exposure of hemiacetals to 81 activated derivatives of phosphoric acid... 

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