Studies on Steroidal Compounds. XII. Stereochemistry of 1, 4-Addition of Grignard Reagent for α, β-Unsaturated Steroidal Ketones. Grignard Reaction of 3β-Hydroxycholest-4-en-6-one

The Grignard reaction of 3β-hydroxycholest-4-en-6-one (V) was undertaken in the presence of cuprous chloride or cupric acetate. 1, 4-Addition product was isolated, and its structure was proved to be 3β-hydroxy-4β-methyl-5α-cholestan-6-one (VI). Some transformations related to this compound were made. From observations of the Grignard reaction and other reactions of α, β-unsaturated steroidal ketones reported in literature, it may be concluded that the configuration of alkyl group newly introduced by 1, 4-addition should be axially oriented.