Synthesis of Glycoborine, Glybomine A and B, the Phytoalexin Carbalexin A and the β‐Adrenoreceptor Antagonists Carazolol and Carvedilol

We describe a regioselective synthesis of 4‐ or 5‐substituted carbazoles by oxidative cyclisation of meta ‐oxygen‐substituted N ‐phenylanilines. Using the regiodirecting effect of a pivaloyloxy group, we prepared 4‐hydroxycarbazole, a precursor for the enantiospecific synthesis of the β‐adrenoreceptor antagonists (−)‐( S )‐carazolol ( 5 ) and (−)‐( S )‐carvedilol ( 6 ). Regioselective palladium(II)‐catalysed cyclisation of different diarylamines led to total synthesis of glycoborine ( 7 ) and the first total syntheses of the phytoalexin carbalexin A ( 8 ), glybomine A ( 9 ) and glybomine B ( 10 ). For glybomine B ( 10 ), a 5‐hydroxycarbazole was converted into the corresponding triflate and utilized for introduction of a prenyl substituent.