Energy barriers considering the Houk–List–Tang–Wo mechanism in cyclohexanone computed using B2-PLYP-DNLPO/def2-TZVPP and CCSD-DLPNO/def2-TZVPP methods on B3LYP-D3/6-31G(d,p) geometries. ΔG^CMPX and ΔG^CMPX label the stabilization energies and free energies of the pre-reaction complexes; ΔE^# and ΔG^# label the transition state energies and free energies with respect to the pre-reaction complex; ΔE^R and ΔG^R the energy differences between the product complex and the pre-reaction complex. Energies are in kcal mol⁻¹.

Product[b]	ΔECMPX	ΔE#	ΔER	ΔGCMPX	ΔG#	ΔGR
DNLPO-B2-PLYP
(S,R)	−13.32	9.11	9.15	−10.66	11.14	11.54
(S,S)	−14.50	12.05	12.43	−10.93	14.53	15.27
(R,S)	−12.69	12.03	7.74	−10.83	15.23	12.56
(R,R)	−11.78	15.19	11.66	−8.97	19.10	17.99
DLPNO-CCSD
(S,R)	−11.22	12.23	9.70	−8.56	14.26	12.09
(S,S)	−12.32	14.12	12.91	−8.75	16.60	15.75
(R,S)	−12.59	17.18	6.70	−10.74	20.38	11.52
(R,R)	−10.56	20.53	10.04	−7.75	24.43	16.38