Science of Synthesis

Li, D.-D.; Wang, G.-W., Science of Synthesis: Catalytic Transformations via C—H Activation, (2015) 2, 344.

Aryl ethers are a widespread motif in a broad range of natural products, pharmaceuticals, agrochemicals, and organic materials, and consequently there has been a considerable amount of research into their synthesis.[‌50‌–‌54‌] One possibility for forming ether bonds is via the reaction of alcohols with appropriate electrophiles. Despite the fact that various protocols have already been established, novel methodologies for C—O bond formation are still of interest; the formation of alkyl aryl ethers by activation of aromatic C—H bonds has been scarcely presented and remains a challenging task.

Me 8888, eee Meeeeee eeeee eeeeeeeee eee eeeeeeeee(MM)-eeeeeeeee eeeeeeeee ee eeeee[e]eeeeeeeee (‌Meeeee 88‌).[‌88‌] Mee eeeeeeee ee eeeee[e]eeeeeeeee eeee (eeeeeeeeeeeee)eeeeeee/eeeeeeeee eeeeeeeee(MM) ee eeeeeee eeeeeeee eeeeeeeeeeeeeeee eeeeeeee eee eeeeeeeeeeeee eeeee eeeeee eeeeeeeee eeeeee, eeeee, eeeeeeeee, eee 8,8,8-eeeeeeeeeeeeee eeeeee.

‌Meeeee 88‌ Meeeeeeee(MM) Meeeeee Meeeeeeee Meeeeeeeeeeeee ee Meeee[e]eeeeeeeee M—M Meeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeee, eee eeee eeeee eeeeeeeee eee eeeeeeeee(MM) eeeeeee eeeeeeeee eeeeeeeeeeeeee ee eeeee M—M eeeee (‌Meeee 8‌).[‌88‌] Meee M—M eeee eeeeeeeeeeeee eeee Meeee ee eeeeeeeee eeeeeeeeee ee eee eeeeeee eee ee eeeeeee ee eeeeeee eeeeeeeee eeeeeeeeeeeee, eeeee-eeeeeeeeeee, eee eeee-eeeeeeeeeee eeeee eeeeeeeeee eeee ee eeeee eeeee ee eeeeeeeeeeeee ee eee eeeeeeeee eeeee. Meeeeeeeeee, eeee, eee eeeeeeeeeeeeeee eeeeee Meeee eee eeeeee ee ee e eeeeeeeeeeee eeeeeeeee eeeeeeee eeeeeee ee eeeee eeeeeeeeeeeeeee, eee eeeeeeee eeee eeeeeeeeee-eeeee eeeeeeeee ee eee eeeeeeeee(MM) eeeeeee eeeeeeeee eeeeeeeeeeeeee.

‌Meeee 8‌ Meeeeeeee(MM) Meeeeee Meeeeeeee Meeeeeeee ee Meee Meeeee Meeeee eeee Meeee ee Meeeeeeee Meeeeeeeee ee Meeeeeee[‌88‌]

Meeeeeeee	Meeeeeeeee	Meeeeee	Meeee (%)	Mee
	Me(MMe)8 (88 eee%), Meeee (8 eeeee), MeMM, ee, 88 e, eeee 88 °M, 88 e		88	[‌88‌]
	Me(MMe)8 (88 eee%), Meeee (8 eeeee), MeMM, ee, 88 e, eeee 88 °M, 88 e		88	[‌88‌]
	Me(MMe)8 (8 eee%), M8M8M8 (8 eeeee), MeMM, ee, 88 e, eeee 88 °M, 88 e		88	[‌88‌]
	Me(MMe)8 (88 eee%), M8M8M8 (8 eeeee), MeMM, ee, 88 e, eeee 88 °M, 88 e		88	[‌88‌]
	Me(MMe)8 (88 eee%), M8M8M8 (8 eeeee), MeMM, ee, 88 e, eeee 88 °M, 88 e		88	[‌88‌]
	Me(MMe)8 (8 eee%), Meeee (8 eeeee), MeMM, ee, 88 e, eeee 88 °M, 88 e		88	[‌88‌]

Me 8888, eee Meee eeeee eeeeeeeeeeee eee eeeeeeeee-eeeeeeeee eeeee-eeeeeeeeeeee ee eeeeeeee M—M eeeee eeeee M-eeeeeeeeeeee ee e eeeeeeeee eeeee (‌Meeeee 88‌).[‌88‌] Meeeeee M-eeeeeeeeeeeeeeeee eeee eeeeee eeeeeeee-eeeeeeee ee eeeeeeee-eeeeeeeeeee eeeeee eee ee eeeeeeeeeee eeeeeeeeeee eeee eeeeeeee eee eeeeeee eeeee eeeeeeeee eeeeeeeeee ee eee eeeeeee, eeeeeeeee eeeeeeee ‌88‌. Meee eeeeeeeee-eeeeeeeee eeeeeeeeeeee ee M-eeeeeeeeeeeeeeeee eee eeeeeeee eeeeeeeeee eeeeee eeee ee eeeeee, eeeee, eeeee, eeeee, eee eeeee eeeeee.

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee Meeeee eeeee-Meeeeeeeeeee ee M-Meeeeeeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Me 8888, eee Meee eeeee eeeeeeee eee eeeeeeeee-eeeeeeeee eeeee-eeeeeeeeeeee ee M-eeeeeeeeeeee (eeeeeeee) eeee eeee eeeeeee eee eeeeeeeee eeeeeeee (‌Meeeee 88‌).[‌88‌] Meee eeeeeeeeeeee eeeeeeee ee eeeeeeeee eeeeeeeeeeeeeee eeee eeee eeeeeeeee eeeeeeeeee ee eee eeeeeee eeeeeeee eeee ee eeee eeeeeeeeeee ee eeee eeeee eee eeeeeee eeeee eeee eeeeee ‌88‌ ee eeeeeeee ee eeee eeeeee. Me eee eeeee eeee eeeeeeeeeeeeeee eeee ee eeeeeee eee eee eeeeeee ee eeee eeeeeeeeeeeeee.

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee Meeeeeee eeeee-Meeeeeeeeeee ee M-Meeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Mee eeeeeeee eee eeeeeeeee ee 88 °M.

e 8 eM ee eeeeeee eee eeee.

e MeMM eee eeee eeeeeee ee MeMM.

Meeeeeee, Mee eee ee-eeeeeee eeeeeeee eee eeeeeeeee(MM) eeeeeee eeeeeeeee eeeeeeeeeeee ee eeeeeeeeeeeeeeeeee eee M(ee8)—M eeee eeeeeeeeee (‌Meeeee 88‌).[‌88‌] Meee eee eee eeeee eeeeeee ee eeeeeeeeee-eeeee-eeeeeeeee M—M eeee eeeeeeeee eeeee eeeee ee eee eeeeeeeee eeeee eee eeeeeeee eeee eeeeeeeeee eee e eeee eeeee ee eeeeeeeeeeeeeeeeee.

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee Meeeee eeeee-Meeeeeeeeeee ee Meeeeeeeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeeeeeeee eeeeeee.

e Meeeeeeeeeeeeeee/eeeeeeeeeeeeee eeeeeee eeeeeee (eeeee 88:88).

e Meeeeeeeeeeeeeee/eeeeeeeeeeeeee eeeeeee eeeeeee (eeeee 88:88).

e Meeeeeeeeeeeeeee/eeeeeeeeeeeeee eeeeeee eeeeeee (eeeee 88:88).

Me 8888, eee Meeee eeeee eeeeeeee eee eeeeeeeeeeee ee eeeeee eeeeeeee ee 8,8-eeeeeeeeeeeeeeeeeeee (‌Meeeee 88‌).[‌88‌] Me eee eeeeeeee ee 8 eee% eeeeeeeee(MM) eeeeeee eee e eeeeeeeeeeeeee eeeeee ee (eeeeeeeeeeeee)eeeeeee, 8-eeee-8,8-eeeeeeeeeeeeeeeeeeee eeeeeee eeeeeeeeeeeee eee eeeeeeeeeeee ee eeeee ee M—M eeeeeeeeee ee eeeeeee eee eeeeeeeeeeeee 8-(8-eeeeeeeeee)-8,8-eeeeeeeeeeeeeeeeeee eeeeeeeeeee ‌88‌ ee eeee eeeeee eeee eeee eeeeeeeeeeeeeeee.

‌Meeeee 88‌ Meeeeeeeeeee ee 8-Meee-8,8-eeeeeeeeeeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeee eeeeeeeeeeee eeee eeee eeee eeee ee eee eeeeeeeee eeeee eee eee eeeeeeeeeeee ee M(ee8)—M eeeee. Me 8888, Meeee, Meeeee, eee ee-eeeeeee eeeeeeee eee eeeeeeeee-eeeeeeeee eeeee-eeeeeeeeeeee eeeeeeee ee 8-eeeeeeeeeeeeeeeeee ee eeeeeeeee eeee eeeeeeeee(MM) eeeeeee/Meeee/eeeeeeeee eeeeeeeee ee eeeeeeee (‌Meeeee 88‌).[‌88‌] Meeeeeeeee eeee eeee eeeeeeee-eeeeeeee eee eeeeeeee-eeeeeeeeeee eeeeee, eeee ee eeeeee, eeeeeee, eeeeee, eee eeeeeeeeeeeeeee, eeeeeee eeeeee eeeeeeeee ee eeeeee eee eeeeeeeeeeeee eeeee-eeeeee eeeeeeee ‌88‌ ee eeeeeeee ee eeee eeeeee. Mee eeeeeeeeeee eeeeeeeee eeee eeeeeeeee eee eeeee eeeeeeeee eeeeeeee ee eeeeeeee eeeee eeeeee eeee eeeee.

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee M—M Meeeeeeeee/eeeee-Meeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeee, eee Meeee eeeee eee eeeeeeeee eee eeeeeeeee-eeeeeeeee eeeee-eeeeeeeeeeee ee 8-eeee-8,8,8-eeeeeeeee (‌Meeeee 88‌). M eeeeeee ee 8-eeee-8,8,8-eeeeeeeee eee ee eeeeeee eeee eeee eeeeeee eee eeeeeeeee eeeeeeee. Me eeeeeeee, eeee eeeee eeeeeeee-eeeeeeeeee eeeeeeeeeeee eeeeeeeee eeeeee eeee eeee eeeeeeee (‌Meeee 8‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee eeeee-Meeeeeeeeeee ee 8-Meee-8,8,8-eeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e 88 eeeee ee eeeeeee eee eeee.

e 8 eeeee ee eeeeeee eee eeee.

‌Meeee 8‌ Meeeeeeee-Meeeeeeee eeeee-Meeeeeeeeeeee Meeee Meeee Meeeeeeeeeee Meeeeeeee Meeeee[‌88‌]

Meeeeeeee	Meeeeee	Meeee (%)	Mee
		88	[‌88‌]
		88	[‌88‌]
		88	[‌88‌]
	eeee	–	[‌88‌]

Mee eeeeeeeee-eeeeeeeee eeeeeeeeeeee ee eeee M—M eeeee eeeee e eeeeeeeee eeeeeeeee eeeee eee eeee eeee eeeeeeeee ee e eee eeeeeeeeeee. Mee Meeee eeeee eee eeeeeeeee eee eeeee-eeeeeeeeeeeee ee M-(8-eeeeeeeeeeeee)eeeeeeeeee (‌Meeeee 88‌).[‌88‌] Meee eeeeeeee eeee e eeeeeeeee eeeeee ee eeeeeeeee(MM) eeeeeee (88 eee%) eee e eeeeeeeeeeeeee eeeeee ee (eeeeeeeeeeeee)eeeeeee ee eeeeeeee ee eeeeeee eee eeeeeeeeeeeee 8-eeeeeeeeeeeeeeeee ‌88‌ ee eeee eeeeee. Me eeeee eee eeeeeeee-eeee ee eeee ee eeeeeeee-eeeeeeeee eeeeeeeeee.

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee Meeeeeeeeeeee ee M-(8-Meeeeeeeeeeee)eeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Mee Meee eeeee eee eeeeeeee eee eeeeeeeee-eeeeeeeee, eeeeeeee-8-eeeeeeeeeee (eeeeeeeeeeee) eeeeeeee eeeeeeeeeeee ee eeee M(ee8)—M eeeee ee eeeeee eeeeeeeee (‌Meeeee 88‌).[‌88‌] Mee γ-eeeee M—M eeeee ee eeeeee eeeeeeeeeeeee ‌88‌ (e = 8) eee ee eeeeeee eeeeeeee eeee e eeeeeee ee eeeeee eeeeee. Meee eeeeeeee-eeee eee eeeeeeee-eeeeeeeee eeeeeeeeee eeeeeee eeee ee eeeeeeeee eeeeee ee eeee eeeee eeeeeeee. Meee 8.8 eeeeeeeeeee ee (eeeeeeeeeeeee)eeeeeee ee eeeeeeee eee eeeeeeeeeeeeeeee, eeeee eeeeeeeeee eeee eee eeeee-M—M eeeee eeeee eeeeeeeee eeeeeeee eeee 8.8 eeeeeeeeeee ee (eeeeeeeeeeeee)eeeeeee. Meeeeeeee, (8-eeeeeeeee)eeeee eeeeeeeeee ‌88‌ (e = 8) eee ee eeeeeeeeeee ee eee δ-eeeee M—M eeeeeeee eeeee eee eeeeeeee eeeeeeee eeeeeeeeee.

‌Meeeee 88‌ Meeeeeeeeeee ee σ-M(ee8)—M Meeee ee Meeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeeeeeeee eeeeeee.

Mee Mee eeeee eee eeeeeeeee eee eeeeeeeee-eeeeeeeee eeeeeeeeeeee ee eeeeeeeeeee eeee M—M eeeee eeeee eeeeeee eeeeeeeee eeeeeeeee eeeee (‌Meeeee 88‌).[‌88‌] Meeeeee eeeeeeeeeeee ee eee M—M eeeee β ee eee eeeeeeeee eeeee, γ-eeeeeeeeeeee eee eeee ee eeeeeeee, eeeeeeee eeee ee eeeeeeee β-M—M eeeee eee eeeeeee. Meeeeeeeeeeee eeeeeeee ‌88‌ eee ‌88‌ eee eeeeeeee ee eeeeeeee ee eeee eeeeee, eeeeee ee eeeee eeee eeeeeeeeee eeeeeee e eeee-eeeeeeeeeee, eeeee eeee ee eee eeeeeeeeeeeeeeeeee eeeeeeee.

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee Meeeeeeeeeee ee M(ee8)—M Meeee Meeee e Meeeeeeee Meeeeeeee Meeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeee ee eeeeeeeeeeeeeee eeeeeee; 8.8 eeeee ee MeM(MMe)8 eee eeee.

e 88% eeeee ee eee eeeeeeeeeeeeeee eeeeeee eee eeee eeeeeeee.

‌Meeeeeeeeee 88M‌

e Meeee ee eeeeeeeeeeeeeee eeeeeee.

Meeeeeeeeeee Meeeeeeee

8-Meeeee-M-eeeeeeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeee ee eee M-eeeeeeeeeeeeeeee (8.88 eeee), Me(MMe)8 (8.8 ee, 8.8888 eeee), M8M8M8 (888 ee, 8.8 eeee), eee 8-Å eeeeeeeee eeeeee (88 ee) ee eeeeeee eeeeeeeee eeeeeee (8 eM) ee 88 °M eee eeeee MeMM, MeMM, ee eMeMM (8 eM). Mee eeeeeeee eee eeeeeeeee ee MMM. Meee eeeeeeeeee, eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeee ee e eeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 8:8) ee eeeeee eee eeeeeee eeeeeee.

eeeee-Meeeeeeeeee Meee M-[8-(8-Meeeeee)eeeeee-8-ee]eeeeee ‌88‌ eee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee eeeeeeeee (8.8 eeee), Me(MMe)8 (8.8 ee, 88 eee%), MeM(MMe)8 (888 ee, 8.8 eeee), eeeeeee (8.8 eM), eee e-eeeeee (8.8 eM) ee e 88-eM Meeeeee eeee (eeeeee eeee M8) eee eeeeee ee 88 °M eee 88 e. Mee eeeeeee eee eeeeee ee ee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee ee eeee eee eeeeeee eeeeeee.

References