Enantioselective synthesis of a key "A-ring" intermediate for the preparation of 1alpha-fluoro vitamin D3 analogues

1Alpha-fluoro A-ring dienol 2, a useful building block for the preparation of fluorinated vitamin D3 analogues, was synthesized in eight steps from 4-{tert-butyldimethylsilyl]oxy}cyclohexanone. The most distinctive synthetic development to emerge from this new synthesis is an unprecedented substrate-controlled diastereoselective fluorodesilylation of an advanced dienylsilane intermediate. This is the first enantioselective route to compound 2 relying on the use of an electrophilic fluorinating reagent.