Table 1.

Results of the tandem catalytic cleavage of β‐O‐4 model compounds 1 a–1 d and major products observed.^[a]

Entry	β‐O‐4	LA[b]	T	Conv.[c]	Product yield [%]
	model	[mol %]	[°C]	[%]	2	3	4	5	7
1	1a	10	200	57	24	47	–	2	–
2	1a	10[d]	200	100	‐	63	–	–	9
3	1b	10	200	96	65	77	–	–	1
4	1b	10	175	99	37	81	–	–	17
5	1b	5	175	99	66	85	–	–	4
6	1b	2.5	175	92	36	41	3	44	–
7	1b	5[e]	175	99	5	84	–	–	31
8	1b	2.5[e]	175	98	45	61	–	25	–
9	1c	5	175	97	67	71	3	4	–
10	1c	2.5	175	39	7	12	8	16	–
11	1d	5	175	100	51	88	–	–	3

[a] Conditions: 2.4 mmol substrate, 2.5 mol % [Rh(cod)Cl]₂, 2:1 dppp/Rh, Sc(OTf)₃ [or In(OTf)₃] as listed; 175–200 °C, 2 h, 22 mL 9:1 1,4‐dioxane/water; yields determined by GC. [b] Lewis acid. [c] Conversion (%). [d] Only Sc(OTf)₃, no [Rh(cod)Cl]₂. [e] In(OTf)₃.