Table 1.

Optimization of template

entry	template	R1	R2	yield (%) (mono)b	yield(%) (di)b	selectivity m:p:oc	entry	template	R1	R2	yield (%) (mono)b	yield (%) (di)b	selectivity m:p:oc
1d	3a	tBu	H	trace	0	—	6	6	tBu	—(CH2)4—	50	11	88:7:5
2e,f	3a	tBu	H	4	0	56:26:18	7	7	tBu	—(CH2)5—	51	15	91:5:4
3	3a	tBu	H	15	0	59:33:8	8	8a	tBu	iBu	67	23	>95:5(p+o)
4	4	tBu	Me	60	17	91:7:2	9g	9	H	iBu	—	—	—
5	5	tBu	Et	52	16	93:6:1	10	10	Me	iBu	39	10	91:8:1

^a Unless otherwise noted, the reaction conditions were as follows: benzyl ethers 3–10 (0.05 mmol), olefin 11a (1.5 equiv.), Pd(OPiv)₂ (10 mol%), Ag(OPiv) (2.1 equiv.), DCE (0.5 mL), 90 °C, 18 h.

^bIsolated yield after purification by silica gel column chromatography.

^cm:p:o denotes the ratio of meta:para:ortho mono-olefinated products, as determined by ¹H NMR analysis of the unpurified reaction mixture.

^dO₂ was used as the oxidant instead of Ag(OPiv).

^ePd(OAc)₂ and Ag(OAc) were used instead of Pd(OPiv)₂ and Ag(OPiv) respectively.

^fNMR conversion was determined by using o-xylene as an internal standard.

^gC–H olefination occurred on both the arene substrate and on the template with a combined yield of approximately 20% yield.

Abbreviations: DCE, 1,2-dichloroethane; Me, methyl; Et, ethyl; ^tBu, tert-butyl; OPiv, pivalate.