Relative enthalpies (ΔH, in kcal mol⁻¹), Gibbs free energies (ΔG, in kcal mol⁻¹) and entropies (ΔS, in cal mol⁻¹ K⁻¹) computed using B3LYP/6-31G(d) method in solvents for TSs and CAs involved in the 32CA reactions of phosphorinium-3-olates 1a and 1b with MMA.

	THF			EtOH
	ΔH	ΔG	ΔS	ΔH	ΔG	ΔS
1a + MMA
TS6n-H	14.1	27.6	−45.3	14.5	28.1	−45.6
TS6x-H	12.1	25.3	−44.3	12.9	26.1	−44.2
TS7n-H	16.9	31.3	−48.3	17.3	31.7	−48.1
TS7x-H	13.8	27.8	−47.2	14.4	28.5	−47.1
CA6n-H	−38.6	−23.1	−51.9	−37.6	−22.1	−51.8
CA6x-H	−38.5	−23.1	−51.6	−37.4	−22.0	−51.5
CA7n-H	−37.8	−22.3	−52.0	−36.8	−21.3	−52.0
CA7x-H	−38.0	−22.7	−51.5	−36.9	−21.5	−51.6
1b + MMA
TS6n-Me	18.8	33.2	−48.3	19.2	33.6	−48.6
TS6x-Me	16.3	30.8	−48.4	17.3	31.8	−48.7
TS7n-Me	22.2	36.7	−48.6	22.7	37.3	−49.0
TS7x-Me	18.7	33.7	−50.4	19.4	34.4	−50.3
CA6n-Me	−29.7	−13.1	−55.5	−28.6	−12.1	−55.5
CA6x-Me	−30.7	−14.2	−55.4	−29.5	−13.0	−55.5
CA7n-Me	−29.2	−12.8	−55.1	−28.2	−11.7	−55.4
CA7x-Me	−30.5	−14.0	−55.3	−29.3	−12.8	−55.4