Table 3.

a. Aryl substituent effects on rearrangement (thermodynamic parameters).
Entry		R	σ	Keq	ΔGexp (kcal/mol)
18a	18b	N(CH3)2	−0.83	(40.5)a	(−2.2)a
19a	19b	OCH3	−0.27	19.4 ± 0.34	−1.73 ± 0.01
11a	11b	n-Bu	−0.16	8.71 ± 0.15	−1.26 ± 0.01
20a	20b	H	0.00	4.32 ± 0.08	−0.85 ± 0.01
21a	21b	Ph	0.01	3.24 ± 0.06	−0.68 ± 0.01
22a	22b	F	0.06	3.61 ± 0.06	−0.75 ± 0.01
23a	23b	Cl	0.23	1.48 ± 0.03	−0.23 ± 0.01
24a	24b	CHO	0.42	0.24b	0.83 ± 0.01
25a	18b	CN	0.66	0.09b	1.43 ± 0.01

b. Aryl substituent effects on rearrangement (kinetic parameters).
Entry		R	σ	Kf+ra	Kfa
18a	18b	N(CH3)2	−0.83	>10	>11
19a	19b	OCH3	−0.27	3.35 ± 0.13	3.93 ± 0.14
11a	11b	n-Bu	−0.16	1.50 ± 0.05	1.66 ± 0.06
20a	20b	H	0.00	1.00 ± 0.03	1.00 ± 0.04
21a	21b	Ph	0.01	1.02 ± 0.04	0.96 ± 0.03
22a	22b	F	0.06	1.01 ± 0.05	0.97 ± 0.03
23a	23b	Cl	0.23	0.86 ± 0.04	0.63 ± 0.02
24a	24b	CHO	0.42	0.99 ± 0.05	0.24 ± 0.01
25a	18b	CN	0.66	-b	-b

^aFrom a first-order kinetic model

^bEstimated error is less than ± 0.01.

^aRelative to 20a in THF-d₈.

^bKinetics unreliable.