Table 4. Relative energies of the eight diastereomeric transition states for the benzoin condensation with catalyst 4.

	Transition-state geometry*
Catalyst	Enolamine	Enolamine face	Aldehyde face	Product configuration	ΔGrel, kcal/mol†
S,S	E	si	si [TS7]‡	R	0
S,S	E	si	re [TS8]‡	S	4.0
S,S	E	re	si	R	4.1
S,S	E	re	re	S	6.3
S,S	Z	re	re	S	8.8
S,S	Z	si	re	S	9.0
S,S	Z	si	si	R	10.1
S,S	Z	re	si	R	12.9

^*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. 8.