Synthesis of 3β,21-dihydroxypregna-5,7-dien-20-one (4) and its UVB-driven photolysis to vitamin D, tachysterol and lumisterol analogues. Reagents and conditions: (a) Ac2O, microwave, p-toluenesulfonic acid monohydrate; (b) Dibromantin, 2,2′-azobisisobutyronitrile, benzene/hexane (1:1), 100°C, reflux; (c) Bu4NBr, Bu4NF, THF, room temperature; (d) K2CO3, MeOH-THF, H2O, argon, room temperature.