. 2020 Sep 22;11(41):11307–11314. doi: 10.1039/d0sc03409f

Gibbs free energies of stationary points in the Pd-catalyzed intramolecular hydroamination of 1a–d. All energy values (in kcal mol⁻¹) are relative to IM1. Bold numbers indicate the most favorable mechanisms in the nucleopalladation step.


Entry	Alkenyl amine	(n + 3)-Exo-trig			(n + 4)-Endo-trig	(n + 3)-Exo-trig
		syn-Nucleo-palladation TS		anti-Nucleo-palladation TS	anti-Nucleo-palladation TS	Pallada-cycle	Protode-palladation TS	β-Hydride elimination TS
		TS2	TS5	TS6	TS7	IM3	TS3	TS4
1	1a (n = 1)	31.0	29.3	Cannot locate	28.0	21.8^a	39.6^a	37.6
2	1b (n = 2)	19.7	21.8	24.0	24.6	5.8	22.0	24.2
3	1c (n = 3)	23.3	21.7	24.9	32.2	5.7	22.7	23.9
4	1d (n = 4)	27.1	29.1	31.3	Cannot locate	8.1	24.5	26.9

In the reaction with 1a, the 5-endo-trig regioisomeric pathway is more favorable. The Gibbs free energies of the palladacycle and the protodepalladation TS in the 5-endo-trig pathway with 1a are 9.2 and 29.4 kcal mol⁻¹, respectively.

Gibbs free energies of stationary points in the Pd-catalyzed intramolecular hydroamination of 1a–d. All energy values (in kcal mol−1) are relative to IM1. Bold numbers indicate the most favorable mechanisms in the nucleopalladation step.

Gibbs free energies of stationary points in the Pd-catalyzed intramolecular hydroamination of 1a–d. All energy values (in kcal mol⁻¹) are relative to IM1. Bold numbers indicate the most favorable mechanisms in the nucleopalladation step.