Comparison of calculated to experimental ΔΔG^‡ values.

Entry	Parent compound	Experimental ΔΔG‡a (kcal mol−1)	Calculated ΔΔG‡b (kcal mol−1)
1		−0.82	−3.33
2		−0.69	−1.09
3		≤−1.77	−3.74
4		−1.56	−2.98
5		−1.39	−2.06
6		−1.52	+0.35
7		−0.41	+2.24
8		+0.38	+1.04

^aΔΔG^‡ = −RT ln(γ-chlorinated product/δ-chlorinated product) ad determined by ¹H or ¹⁹F NMR of crude reaction mixture.

^bΔΔG^‡ = (ΔG(1,6-HAT TS) − ΔG(1,7-HAT TS)) as determined from the calculated Gibbs free energies using uB3LYP/6-31+G(d,p).