Phosphoric acid derivatives amines

Carboxylic acids can also be activated by the formation of mixed anhydrides with various phosphoric acid derivatives. Diphenyl phosphoryl azide, for example, is an effective reagent for conversion of amines to amides.140 The proposed mechanism involves formation of the acyl azide as a reactive intermediate. 

Carbon-13 shifts of representative phosphines [364], phosphonium salts [365], phospho-nium ylides [365, 366], diphosphines [367], phosphonates [368], phosphorous and phosphoric acid derivatives [369] are summarized in Table 4.49. I3C shift data of some group V organoelement compounds are compared in Table 4.50. It turns out that a sp3 carbon nuclei of phosphines and arsines are shielded (0-25 ppm) relative to those of amines (30-60 ppm), as expected from the heavy atom effect, sp2 carbons of CC double bonds behave correspondingly, as shown for the triphenyl derivatives in Table 4.50, with... 

Fig. 14.7. A scheme of the bilayer lipid membrane. The black circles indicate the polar heads (the hydrophilic part) consisting of phosphoric acid, ethanol amine, and analogue derivatives. The wavy lines are the long alkyl chains of fatty acids (the hydrophobic part) (Reprinted from J. Koryta, Ions, Electrodes and Membranes, Fig. 83. Copyright J. Wiley Sons, Ltd. 1991. Reproduced with permission of J. Wiley Sons, Ltd.)...

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... 

Substrates usefully employed in Mannich reactions are, in general, XH compounds having nucleophilic properties, with X being equal to C, N, or other heteroatoms (Fig. 4). In particular, CH compounds are suitably activated saturated and unsaturated derivatives, and NH substrates may be amines, amides, hetcrocyclcs, etc. Out of OH sub-stratcs, alcohols are mainly able to give stable Mannich products. Sulfur- and phosphorus-containing substrates are XH derivatives having the H atom bonded to the hetcroatom in the lower oxidation state, i.e., thiols, sulfinic acids, and, respectively, phosphine and phosphorous acid derivatives. As and Se compounds have also been successfully used. All these substrates are listed in more detail in Sec. D of this chapter. 

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. 

Gong, et al. reported a phosphoric acid derivative 258 catalyzed asymmetric three-component formal [4 + 2] cycloaddition reaction of azlactones 257, a,p-unsaturated aldehydes 28, and primary amines 256 to give the 3-amino-3, 4-dihydropyridinones 259 with high enantioselectivities (up to 96% ee), Scheme 3.82 [104],... 

More recently. List and co-workers [169], have reported the asymmetric epox-idation of cyclic enones, using a chiral primary diamine (111) and a phosphoric acid derived from BINOL (112) (Scheme 12.29). With H2O2 as oxidant, the epoxides were obtained in good yields (63-82%) and moderate to good enantioselectivities (78-98%). They also tested amine 113, which provided better ee s (92 to 99%) and slightly lower yields (49-85% (Scheme 12.29). 

In 2008, List s group developed an epoxidation using asymmetric counteranion-directed catalysis (ACDC) [177]. In this work, the epoxidation of 1,2-disubstituted enals (33) and (3,(3-disubstituted, a, 3-unsaturated aldehydes (115) was explored. Instead of using a chiral amine (e.g. Jprgensen-Hayashi s catalyst), an achiral amine and a chiral counteranion (a phosphoric acid derived from BINOL), were employed. 

Antilla et al synthesized a novel phosphoric acid derivative (48), starting from (R)-VAPOL (vaulted biphenanthrol) [181], and demonstrated its catalytic activity in the addition of sulfonamide to aldimines, giving rise to protected aminals, which have been incorporated into peptide chains as retro-inverso peptide mimics. (Scheme 2.105) [182]... 

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

Nucleophilic attack of amines on fully esterified derivatives of phosphoric acid and its thio-analogues may in general occur at phosphorus or carbon. In an attempt to correlate the rates with structural factors, a study has been reported on a series of compounds of the type (49), ... 

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... 

VAPOL-derived phosphoric acid 11 was shown to catalyze the amidation of Boc-protected N-aryl imines with sulfonamide, phthaUmide, and maleimide nucleophiles to furnish the corresponding chiral aminals in excellent yields and ee s (Scheme 5.29) [52, 53]. This represents the first general catalytic and asymmetric... 

This conclusion has been drawn by Moffatt and Khorana,2 based on limited data. A subsequent, more detailed study [R. K. Ledneva, N. N. Preobrazhenskaya, Z. A. Shabarova, and M. A. Prokof ev, Molek. Biologiya, 5, 264 (1971)] clearly shows an unexpected decrease in the rate of the acid hydrolysis of the phosphor-amidates derived from strong amines. If a similar order of reactivities exists for the pyrophosphate synthesis, the phosphomorpholidate derivative seems close to being the most active. 

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