Diphenyl 1-Aminoalkanephosphonates

Oleksyszyn, Józef; Subotkowska, Lidia; Mastalerz, Przemyslaw

doi:10.1055/s-1979-28903

Cited by 143 publications

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“…One antibody was isolated that accelerated the formation of peptide 8 from the corresponding substrates and was characterized with respect to its substrate specificity and reaction kinetics. MATERIALS Diphenyl 1-(N-carbophenethyloxyamno)ethylphosphonate (10). To a solution ofphosgene in toluene (31 ml, 1.9 M) at 00C was added phenethyl alcohol (6.0 ml, 50 mmol).…”

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“…87-890C. To a stirred solution of the carbamate (3.3 g, 20 mmol) in triphenylphosphite (5.2 ml) and acetic acid (5.0 ml) was added acetaldehyde (1.7 ml, 30 mmol) (10). The reaction was stirred at room temperature for 1 N-(4-Nitrobenzoyl)-1,3-dlaminopropane (11).…”

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“…The mixture was stirred under positive hydrogen pressure for 1 h. The mixture was reduced in vacuo without removal of the catalyst and purified by silica gel chromatography (5% methanol in methylene chloride, Rf = 0.47) to give 19 mg (79%) of 1 as a colorless oil; 'H NMR (500 MHz, C2HC13) 6 Protein-Hapten Conjugates. Hapten 1 (6.8 mg, 10 Ismol) was dissolved in 1.0 ml of tetrahydrofuran, and 56 ,u of 0.20 M thiophosgene (11 ,umol) in tetrahydrofuran was added. After 3 h the reaction was judged to be complete by TLC.…”

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Antibody catalysis of peptide bond formation.

Jacobsen

Schultz

1994

Proc. Natl. Acad. Sci. U.S.A.

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An antibody generated against a neutral phosphonate diester transition-state (TS*) analog catalyzes the formation of an amide bond between a phenylalanyl amino group and an acyl azide derived from L-alanine. The antibody is selective for L-vs. D-alanine and does not catalyze the hydrolysis of the acyl azide to an appreciable degree. A rate acceleration of 10,000-fold relative to the uncatalyzed reaction is observed. The antibody may achieve its catalytic efficiency both by acting as an entropy trap and by stabilizing the deprotonated form of the amine nucleophile. These experiments constitute a first step toward a general strategy for the generation of sequence-specific peptide ligases. We wished to investigate the requirements for catalysis of peptide bond formation using a catalytic antibody. Previously reported studies in this area focused on condensation reactions involving activated esters and-aryl amines (7,8). We have applied a design strategy that was found to be highly successful for bimolecular ester formation (9). Antibodies were generated against the neutral phosphonate diester 1 that contains elements ofthe acyl donor 5, acceptor 7, and leaving group in a tetrahedral geometry mimicking that of the presumed transition state (Fig. la). One antibody was isolated that accelerated the formation of peptide 8 from the corresponding substrates and was characterized with respect to its substrate specificity and reaction kinetics. MATERIALS Diphenyl 1-(N-carbophenethyloxyamno)ethylphosphonate (10). To a solution ofphosgene in toluene (31 ml, 1.9 M) at 00C was added phenethyl alcohol (6.0 ml, 50 mmol). N,NDimethylaniline (6.4 ml, 50 mmol) was added dropwise over a 10-min interval, and after an additional 15 min, 8 ml of methylene chloride was added, and the reaction was warmed to room temperature. After 4 h residual phosgene was removed under reduced pressure, and the crude chloroformate was treated with 2.9 M aqueous ammonia (70 ml) and stirred rapidly for 30 min. The product was extracted into 50 ml of methylene chloride. The 64.94; H 5.69; N 3.29; P, 7.28. Found: C, 64.88; H, 5.71; N, 3.27; P, 7.28. N-(4-Nitrobenzoyl)-1,3-dlaminopropane (11). To a suspension of 4-nitrobenzoyl chloride (7.2 g, 39 mmol) in 150 ml of methylene chloride at OC was added triethylamine (14 ml, 98 mmol) and 3-bromopropylamine hydrobromide (8.6 g, 39 mmol). The solution was warmed to room temperature, and after 15 min the reaction mixture was diluted with 100 ml of methylene chloride and extracted twice with 100-ml portions of 0.1 M HCO and twice with 100-ml portions of 0.1 M NaOH. The The publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked "advertisement" in accordance with 18 U.S.C. §1734 solely to indicate this fact.

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Antibody catalysis of peptide bond formation.

Jacobsen

Schultz

1994

Proc. Natl. Acad. Sci. U.S.A.

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“…The methodology for the preparation of precursors 7a-c, 8a-c and 9a-c is outlined in Scheme 2. The Birum-Oleksyszyn condensation 11,12 of aldehydes 1a-c with triphenyl phosphite and benzyl carbamate afforded Z-protected diphenyl phosphonates 4a-c, enabling access to the first precursors, dimethylesters 8a-c, via transesterification using sodium methanolate. Cleavage of the benzyloxycarbonyl group from compounds 4a-c was achieved by treatment with hydrobromic acid in glacial acetic acid to yield the corresponding salts 5a-c, which were subsequently converted to Boc-protected phosphonates 6a-c by reaction with triethylamine and Boc anhydride.…”

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The synthesis of phosphonic acids derived from homocysteine via transesterification reactions

Pícha¹,

Budêšínský²,

Fiedler³

et al. 2011

Arkivoc

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An efficient methodology for the synthesis of S-substituted derivatives of phosphonohomocysteine has been developed. It starts from the corresponding thiols and is based on a synthetic sequence consisting of (i) the Kabachnik-Fields reaction, (ii) the transesterification of the diphenylphosphoryl moiety and (iii) the acidic deprotection of the phosphoryl and amino groups. The proposed synthetic procedures describing syntheses of phosphonohomocysteine precursors with di-tert-butylphosphoryl and tert-butyloxycarbonylamino groups could be useful for the preparation of novel S-substituted phosphonohomocysteine derivatives.

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“…Diphenyl 1-(phenylmethoxycarbonylamino)ethyl phosphonate 7 was synthesized using triphenyl phosphite 5, benzyl carbamate 6, and aldehyde 4 according to the method of Oleksyszyn 13 and converted by ester exchange in methanol to the dimethyl ester 8. The monomethyl ester 9 was obtained by partial base-catalyzed hydrolysis of dimethyl ester 8 and was subsequently converted by treatment with thionyl chloride in dichloromethane to chlorophosphonate 10.…”

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