Table 1.

Theoretically predicted and experimentally observed enantioselectivities for the thionation of rac‐1, catalyzed by various CPAs.

Entry	Catalyst	ΔΔG ≠ calc [a]	ΔΔG ≠ exp [b]	ee calc [c]	ee exp [d]
1	(R)‐C1	1.9	1.9	92	92
2	(R)‐C2	1.0	0.4	69	31
3	(R)‐C3	0.7	0.3	53	24
4	(R)‐C4	0.4	0.1	33	7
5	(R)‐C5	3.1	2.1	99	94
6	(R)‐C6	3.6	2.3	>99	96
7	(R)‐C7	4.2	2.1	>99	94

[a] ΔΔG ^≠ _calc=ΔG ^≠ ₂−ΔG ^≠ ₁, where ΔG ^≠ ₁ and ΔG ^≠ ₂ were obtained by theoretical calculations. [b] ΔΔG ^≠ _exp is extrapolated from the experimentally observed ee values (ΔΔG ^≠=−RTln[(1−ee)/(1+ee)]). [c] ee value predicted by theoretical calculations. [d] ee values experimentally observed. Energy differences are given in kcal mol⁻¹.