Scheme 7.
Synthesis of β-ketophosphonate 15. a, PMB—Br, Et3N, potassium hexamethyldisilazane, THF, -78°C → 23°C, 13 h, 91%; b, BH3·SMe2, 2-methyl-2-butene, THF, 0°C, 5 h, then H2O2, NaHCO3, 85%; c, SO3·pyridine, DMSO, i-Pr2NEt, CH2Cl2, 0°C, 30 min, 91%; d, Et2Zn (1 M in hexanes), (–)-N,N-dibutylnorephedrine, toluene, 0°C → 23°C, 76 h, 94%, ds = 90:10; e, triethylsilyltrifluoromethanesulfonate, 2,6-lutidine, CH2Cl2, 0°C, 1 h, 94%; f, (MeO)2P(O)CH3, BuLi, THF, -78°C, 30 min, 96%.