Table 2. Relative energies of the eight diastereomeric transition states for the benzoin condensation with catalyst 2.

	Transition-state geometry*
Catalyst	Enolamine	Enolamine face	Aldehyde face	Product configuration	ΔGrel, kcal/mol†
S	E	re	si [TS3]‡	R	0
S	E	si	re [TS4]‡	S	0.7
S	Z	si	re	S	0.8
S	Z	re	re	S	0.8
S	E	si	si	R	1.6
S	E	re	re	S	1.7
S	Z	si	si	R	5.9
S	Z	re	si	R	9.8

^*See Data Set 1 for figures of structures and Cartesian coordinates.

^†Relative energies obtained by single-point B3LYP/6-31G(d) calculations.

^‡Depicted in Fig. 6.