With a range of mono-and di-borylated products accessible their utility was explored. Given the importance of thienyl-C(H)(OH)Ph units in active pharmaceutical ingredients, e.g., tiemonium salts, a one-pot route to these motifs from a thiophene precursor was targeted. The reaction of crude (i.e., made in-situ and taken forward with no purification) Br-thienylBBN (3c) with benzaldehyde proceeded to form 6a in 70% yield (Scheme 1 top) with the alcohol 6b then formed using the previously reported O-BBN hydrolysis conditions (see Fig. ).