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On the Electrophilicity of Cyclic Acylphosphoramidates (CAPAs) Postulated as Intermediates
Author(s) -
Ni Feng,
Gao Xiang,
Zhao ZengXiang,
Huang Chao,
Zhao YuFen
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200900227
Subject(s) - chemistry , phosphoramidate , amino acid , phosphate , reactivity (psychology) , stereochemistry , nucleophile , electrophile , organic chemistry , medicinal chemistry , catalysis , biochemistry , alternative medicine , pathology , medicine
Cyclic acylphosphoramidates (2‐hydroxy‐2‐oxy‐1,3,2‐oxazaphospholidine‐5‐ones, CAPAs) are phosphate‐activated amino acids possessing both a carboxyl–phosphoryl anhydride and a phosphoramidate bond in a ring. They structurally resemble NCAs (amino acid N ‐carboxyanhydrides,Leuchs' anhydrides), which have been extensively investigated. By contrast, the chemistry of CAPAs has remained almost unexplored since it was proposed in a prebiotic reaction of inorganic polyphosphates (PolyPs) with amino acids. In the present work, the bielectrophilicity of α‐CAPAs (Gly‐CAPA, Ala‐CAPA) was identified by isotopic analysis ( 18 O, 15 N) and further proved by trapping α‐CAPA with nucleophiles such as water, amino acids, phosphate and methanol in alkaline media, which yielded N ‐phosphoamino acids and peptide phosphoanhydride and phosphate ester derivatives. By comparison with the reactivity of NCAs, the bielectrophilicity of CAPAs indicates that CAPAs can provide rich chemistry.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)