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Two A-ring stereoisomeric 1-hydroxy-6,7-diaza-19-norvitamin D 3 compounds 7a , 8a and their 25-hydroxylated analogs, 7c , 8c have been prepared starting with enantiomeric trans-3,5-dihydroxycyclohexanones 3c,d and the CD-ring 8-ketones 4a and 4c . 1,25-Dihydroxy azavitamins 7c and 8c are essentially devoid of biological activity, demonstrating the importance of the 5,7-diene structure of vitamin D.

The reaction of Grundmann's ketone 2a with ruthenium tetroxide, generated in situ from ruthenium trichloride and sodium metaperiodate, has been investigated. In addition to the main 25-hydroxylated compound 2b the minor oxidation products have been isolated and identified. The examined catalytic process results in the oxidation of methylene groups and hydroxylation at teriary positions occurring with retention of configuration.

Vitamin D C-22 aldehyde and 1α-hydroxyvitamin D C-22 aldehyde were efficiently synthesized starting from the readily available 22,23-bisnorcholenic acid. The usefulness of the compounds as common intermediates for the synthesis of side chain modified analogues of vitamins D2 and D3 has been demonstrated.