Synthesis of α-fluorinated phosphonates as metabolically stabilized lysophosphatidic acid analogues

ORGN 508

Yong Xu and Glenn D. Prestwich. Department of Medicinal Chemistry, University of Utah, 419 Wakara Way, STE 205, Salt Lake City, UT 84108
Lysophosphatidic acid (LPA) is a naturally occurring phospholipid that exhibits pleiotrophic biological activities, ranging from rapid morphological changes to long-term cellular effects such as induction of gene expression and stimulation of cell proliferation and survival on a wide spectrum of cell types. The preparation of receptor-specific agonists and antagonists for LPA receptors is an active area of ligand design. Recently experimental and theoretic reports indicate that α-monofluoromethylenephosphonate is an excellent phosphate mimic. Therefore, we have developed three methods for the synthesis of α-monofluoromethylenephosphonates as metabolically stabilized LPA analogues: Hydrolytic kinetic resolution (HKR) of a racemic monofluorinated epoxides; Lewis acid catalyzed ring opening of monofluorinated epoxides by alcohol; Hydrogenation of α-fluorovinylphosphonates. The α-monofluoromethylenephosphonate analogues, unique new nonhydrolyzable LPA ligands, showed surprising enantiospecific and receptor-specific biological readouts. One analogue was a long-lived hyperagonist, showing a 1000-fold higher activity than 18:1 LPA for LPA3 receptor and one was a selective LPA1 receptor agonist.