ChemInform Abstract: IMINATION OF CARBONYL‐SUBSTITUTED ALKYLPHOSPHONITES BY PHENYLAZIDE

Abstract

Die Reformatskiisynthese der Ausgangsmaterialien (I) wurde z.T. bereits in früheren Arbeiten der Verfasser beschrieben, z.T. wie für (Ic) wird sie hier abgehandelt.

Staudinger-Phosphonite Reactions for the Chemoselective Transformation of Azido-Containing Peptides and Proteins

“…First, we used the commercially available dimethyl phenylphosphonite ( 2a ), which is however only partially soluble in water. Although reactions of benzyl azide in organic solvents proceed in high yields to the corresponding phosphonamidate (see Supporting Information (SI)), which is in accordance with similar transformations from the literature, , an analogous reaction with a water-soluble unprotected arylazido-peptide 3a delivered only a very moderate conversion of the peptide (see Scheme and Table , entry 1) as monitored by HPLC-MS (see SI). Nevertheless, a phosphonamidate-peptide obtained from 2a did not show signs of decomposition under physiological (pH 7.6–8.2, 26 h) or HPLC conditions (1% AcOH in AcCN/H 2 O, 3 h), indicating the stability of the Staudinger-phosphonite conjugates (see SI).…”

“…Recently, we have identified the Staudinger-phosphite reaction as a chemoselective transformation of azides under physiological conditions. , In the current study, we introduce phosphonites as another type of P(III)-reagents for the chemoselective functionalization of azido-biopolymers. Our main motivation was to employ the high intrinsic reactivity of phosphonites in Staudinger reactions, which have been mainly used for transformations in organic solvents in the past . Additionally, phosphonites have the potential to transfer a single functional module or label that is attached to the carbon chain at phosphorus to an azido-containing biopolymer .…”