Table 3.

Calculated and experimentally observed differences in ligand-coupling transition-state energies [kcal mol⁻¹].

Entry	Nucleophile	Salt	Exptl Ph/Ar ratio[a]	Exptl[b] ΔΔG≠	Calcd[c] ΔΔG≠
1	3	1 a	2.9:1	−0.6	−0.5
2	3	1 e	1:9	+1.3	+0.9
3	6	1 a	1.4:1	−0.3	−0.5
4	6	2 b	3.0:1	−0.9	−1.0
5	9[d]	1 d	2.0:1	−0.4	−0.4
6	9[d]	1 e	only Ph	<−1.8[e]	−2.0

[a] Ratios taken from Tables 1 and 2. [b] Differences in reaction barriers as converted from the observed chemoselectivities based on the Eyring equation. The temperatures of the experiments (Scheme 2) were taken into account during the conversion of the selectivities. [c] Difference in the Gibbs free energies between the lowest-energy transition states that lead to the two products. Room temperature was used for nucleophiles 3 and 9, whereas 130 °C was used for nucleophile 6. [d] Diethyl methylmalonate was modeled as dimethyl methylmalonate. [e] A difference of 1.8 kcal mol⁻¹ corresponds to a 95:5 ratio.