Table 3. Relative energies of the eight diastereomeric transition states for the benzoin condensation with catalyst 3.

	Transition-state geometry*
Catalyst	Enolamine	Enolamine face	Aldehyde face	Product configuration	ΔGrel, kcal/mol†
R	E	si	si [TS5]‡	R	0
R	E	si	re [TS6]‡	S	1.8
R	E	re	re	S	4.9
R	Z	re	si	R	7.3
R	Z	re	re	S	7.9
R	E	re	si	R	8.2
R	Z	si	si	R	10.3
R	Z	si	re	S	11.4

^*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. 7.