Stereoselective syntheses of dolicholide (3), (22R,23R)-2α,3α,22,23-tetrahydroxy-B-homo-7-oxa-5α-ergost-24(28)-en-6-one, and dolichosterone (4), (22R,23R)-2α,3α,22,23-tetrahydroxy-5α-ergost-24(28)-en-6-one, were achieved from the known (22E,24S)-2α,3α-diacetoxy-5α-stigmast-22-en-6-one (5) which is readily available from stigmasterol. The key step in the construction of the (22R,23R)-vicinal diol function in the steroidal side-chain was new and used the method of chelation control.