Preparation of dithienylphospholes by 1,1-carboboration.

In this study the scope of the 1,1-carboboration reaction was extended to the preparation of mixed heterole-based conjugated π-systems. Two arylbis(alkynyl)phosphane starting materials 2 were synthesized bearing two thiophene isomers at the alkyne units and the bulky tipp-substituent (tipp=2,4,6-triisopropylphenyl) at the phosphorous atom. The bis(thienylethynyl)phosphanes 2 were converted into the corresponding 2,5-thienyl-substituted 3-borylphospholes 4 in a double 1,1-carboboration reaction sequence employing the strongly electrophilic B(C6 F5 )3 reagent under mild reaction conditions. Subsequent Suzuki-Miyaura type cross-coupling yielded the corresponding 3-phenylphospholes 7 in a one-pot procedure from phosphanes 2 in high yields. Phospholes 7 were converted into the respective phosphole oxides 8. A photophysical characterization of derivatives 7 and 8 was carried out. The results presented here demonstrate the suitability of the 1,1-carboboration reaction for the preparation of phosphole-/thiophene-based, light-emitting systems.