BiX 3 -Mediated Hydrohalogenations of HDDA Benzynes: An Approach to Polycyclic Aryl Halides.

Here we demonstrate the hydrohalogenation reactions of HDDA benzynes promoted by BiX 3 reagents for the generation of complex aryl halides. All three bismuth(III) halides can act as the source for their respective halides, i.e., Cl - or Br - or I - . The regiochemical preference for hydrohalogenation is dependent on the nature of the substituent present at the diyne terminus but neither on the linker nor on the BiX 3 reagent. The substrate scope for this transformation is broad in terms of the tethers A-B-C and the substituents R 1 and R 2 .