Scope for the 1,3-difluorination of unactivated alkenes with branched substrates, 1(0.6 mmol, 130 mM), 0.5 : 1 [HF] : DCM, rt, 2 h. 5.5HF : amine=1 : 1 3HF NEt3: 9HF.py. Isolated yields of product 2. NMR yields in parentheses, referenced to C6F6 internal standard. Relative stereochemistry assigned through coupling in 19F and 1H NMR (see Supporting Information for details). a) 8HF : pyridine used instead of 5.5HF : amine; b) 6 hr; c) 0.2 mmol of 1; d) 0.4 mmol of 1; e) 0.1 mmol of 1.