REGIOSELECTIVE PALLADIUM(O) CATALYZED AMINATION OF CARBONATES OF ALLYLIC ALPHA-HYDROXYPHOSPHONATES WITH HYDROXYLAMINE DERIVATIVES - A CONVENIENT ROUTE TO PHOSPHONIC-ACIDS RELATED TO THE ANTIBIOTIC FOSMIDOMYCIN

Palladium(0) catalyzed amination of diisopropyl (1-methoxycarbonyloxy- 2-propenyl)phosphonate (I) with tert-butyl (tert-butoxycarbonyloxy)car bamate (BocNHOBoc, 2a), and (N-acetyloxy)acetamide (AcNHOAc, 2b) proce eds regiospecifically and with high (E)-stereoselectivity to give the protected [3-(N-hydroxyamino)-1-propenyl]phosphonates 3a and 3b, respe ctively, in high yields. Hydrogenation of compounds 3a and 3b affords the corresponding propylphosphonates 4. Compounds 3a,b and 4a,b are fu rther converted to precursors and analogues of the phosphonic acid ant ibiotic fosmidomycin.