Tritylamine (Triphenylmethylamine) in Organic Synthesis; I. The Synthesis of<i>N</i>-(Triphenylmethyl)alkanimines, 1-(Triphenylmethylamino)alkylphosphonic Esters, and 1-Aminoalkylphosphonic Acids and Esters

Soroka, Mirosław; Zygmunt, Jan

doi:10.1055/s-1988-27576

Cited by 35 publications

(23 citation statements)

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“…Instead, both diastereomers of the hydrogenated analog of desmethyl dehydrophos (Gly-Leu-AlaP, 3, Fig. 2A) were prepared using previously described methodology (15,22). These peptides incorporate the well known phosphonate analog of alanine, AlaP (23).…”

Section: Resultsmentioning

confidence: 99%

Characterization and structure of DhpI, a phosphonate O -methyltransferase involved in dehydrophos biosynthesis

Lee

Bae

Kuemin

et al. 2010

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

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Phosphonate natural products possess a range of biological activities as a consequence of their ability to mimic phosphate esters or tetrahedral intermediates formed in enzymatic reactions involved in carboxyl group metabolism. The dianionic form of these compounds at pH 7 poses a drawback with respect to their ability to mimic carboxylates and tetrahedral intermediates. Microorganisms producing phosphonates have evolved two solutions to overcome this hurdle: biosynthesis of monoanionic phosphinates containing two P-C bonds or esterification of the phosphonate group. The latter solution was first discovered for the antibiotic dehydrophos that contains a methyl ester of a phosphonodehydroalanine group. We report here the expression, purification, substrate scope, and structure of the O-methyltransferase from the dehydrophos biosynthetic gene cluster. The enzyme utilizes S-adenosylmethionine to methylate a variety of phosphonates including 1-hydroxyethylphosphonate, 1,2-dihydroxyethylphosphonate, and acetyl-1-aminoethylphosphonate. Kinetic analysis showed that the best substrates are tripeptides containing as C-terminal residue a phosphonate analog of alanine suggesting the enzyme acts late in the biosynthesis of dehydrophos. These conclusions are corroborated by the X-ray structure that reveals an active site that can accommodate a tripeptide substrate. Furthermore, the structural studies demonstrate a conformational change brought about by substrate or product binding. Interestingly, the enzyme has low substrate specificity and was used to methylate the clinical antibiotic fosfomycin and the antimalaria clinical candidate fosmidomycin, showing its promise for applications in bioengineering.antibiotics | bioengineering | conformational change | X-ray crystallography | domain-swap

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Section: Resultsmentioning

confidence: 99%

Characterization and structure of DhpI, a phosphonate O -methyltransferase involved in dehydrophos biosynthesis

Lee

Bae

Kuemin

et al. 2010

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

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“…The three-component reaction using dialkyl phosphite 6a-c,t ritylamine, and formaldehyde smoothly produced 7a-c in good yield. [11] The trityl groups of 7a-c were then exchanged with an Nps group by removing the trityl group under acidic conditions followed by treatment with NpsCl. Thus-obtained 8a-c were oxidized with MnO 2 [12] to give the desired imino phosphonates 5a-c.A se xpected, 5a-c, as well as the corresponding imino amide, were sufficiently stable to be purified by silica gelc olumn chromatography.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Synthesis of α‐Amino Phosphonic Acids using Stable Imino Phosphonate as a Universal Precursor

Inokuma

Sakakibara

Someno

et al. 2019

Chemistry A European J

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A practical method for synthesizing chiral α‐amino phosphonic acid derivatives was developed. Readily available and stable N‐o‐nitrophenylsulfenyl (Nps) imino phosphonate was utilized as a substrate for a highly enantioselective Friedel–Crafts‐type addition of indole or pyrrole nucleophiles catalyzed by chiral phosphoric acid. The resulting adduct was easily converted into N‐9‐fluorenylmethyloxycarbonyl (Fmoc) amino phosphonic acid, which is useful for synthesizing peptides containing an amino phosphonic acid.

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“…4 Years ago we introduced successfully tritylamine as an ammonia equivalent in the Mannich type reaction for the synthesis of N-tritylalkanimines and N-trityl-1-aminoalkylphosphonates. 5 We assumed that a highly stereoelectronic hindered trityl group should moderate the reactivity of the amino function, therefore, it should improve regioselectivity and decrease the rate of the ring-opening reaction of epoxides. Moreover, the reaction of epoxides with tritylamine seems to be the easiest way for preparation of N-tritylated β-aminoalcohols (Scheme 1).…”

Section: 3mentioning

confidence: 99%

Tritylamine (triphenylmethylamine) in organic synthesis; II. The reaction of tritylamine with oxiranes – synthesis of N-trityl-β-aminoalcohols

Soroka¹,

Goldeman²

2003

Arkivoc

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Tritylamine (Triphenylmethylamine) in Organic Synthesis; I. The Synthesis ofN-(Triphenylmethyl)alkanimines, 1-(Triphenylmethylamino)alkylphosphonic Esters, and 1-Aminoalkylphosphonic Acids and Esters

Cited by 35 publications

References 0 publications

Characterization and structure of DhpI, a phosphonate O -methyltransferase involved in dehydrophos biosynthesis

Characterization and structure of DhpI, a phosphonate O -methyltransferase involved in dehydrophos biosynthesis

Asymmetric Synthesis of α‐Amino Phosphonic Acids using Stable Imino Phosphonate as a Universal Precursor

Tritylamine (triphenylmethylamine) in organic synthesis; II. The reaction of tritylamine with oxiranes – synthesis of N-trityl-β-aminoalcohols

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