Using 1-fluoroheptane as the HF donor, a range of cyclic and acyclic alkyl-substituted alkynes could be employed in the HF shuttling reaction to afford respective products with moderate to good yields (2a-2m). The reaction scope includes both internal and terminal alkynes substituted by aliphatic groups. Remarkably, substrates with potentially sensitive functional groups were tolerated, including halogens (2e-2g), and a phthalimido group (2h). The reaction is also selective for a single sp 3 C-F moiety, as the trifluoromethyl group can be carried through unscathed (2j) with similar yields to the methylated analogue (2k). Coordinating groups including a benzoate ester (2l), a thiophene ring system (2m) also delivered the gem difluoro products in moderate to good yields. Catalyst poisoning experiments were conducted by added stoichiometric quantities of methyl benzoate, thiophene, and furan, to the standard catalytic procedure. Yields of 1a and 2b ranged from 30-75% and 30-72% respectively in the presence of these additives, and in no case was catalysis completely inhibited. In contrast, addition of pyridine completely shut down the catalytic reactions.