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2.11.3.1 Intermolecular C—O Bond Formation

DOI: 10.1055/sos-SD-218-00206

Li, D.-D.; Wang, G.-W.Science of Synthesis: Catalytic Transformations via C—H Activation, (20152391.

In 2012, the Ackermann group presented ruthenium-catalyzed C(sp2)—H bond oxygenations with weakly coordinating ketones, providing 2-acylphenols 58 (Scheme 82).[‌107‌] The intermolecular oxidative C—O bond-forming reactions are achieved with Oxone, potassium persulfate, or (diacetoxyiodo)benzene as the terminal oxidant and inexpensive ruthenium(III) chloride hydrate [RuCl3(H2O)n] or well-defined (p-cymene)ruthenium(II) 2,4,6-trimethylbenzoate [Ru(O2CMes)2(p-cymene)] as the catalyst. The C(sp2)—H bond hydroxylations exhibit excellent functional-group tolerance and broad scope as well as high chemoselectivity and site selectivity.

Meeeee 88 Meeeeeeee-Meeeeeeee M—M Meeeeeeeeee ee Meeeeeee Meeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
M M 88e [‌888‌]
M Me 88 [‌888‌]
M MM8 88 [‌888‌]
M Me 88 [‌888‌]
M MM8Me 88 [‌888‌]
M M 88 [‌888‌]
M Me 88 [‌888‌]
M Me 88 [‌888‌]
M M 88 [‌888‌]
Me Me 88 [‌888‌]
Me M 88 [‌888‌]
MM8 M 88 [‌888‌]
MMe M 88 [‌888‌]

e Meee MeMe8(M8M)e (8 eee%) eee eeee eeeeeee ee Me(M8MMee)8(e-eeeeee), eee eeeee eee 88%.

Meeee, eee Mee eeeee eeeeeeee e eeeeeee eeeeeeeee-eeeeeeeee M—M eeeeeeeeeee ee eeee eeeeeee. M eeeeeee ee eeeeeeee eeeeeee eee eeeeeeeeeee eeeeeeeeeee eeee eee eeeeeee eeeeee eeeeeeee 88 eeeee eeee eeeeeeeee (Meeeee 88).[‌888‌] Meeeeeee eeeeeeee-eeeeeeeeeee eee eeeeeeee-eeeeeeee eeeeeeeeee eeeeee (eeeee, eeeeeee, eeeee, eeeee, eeeeeee, eeeee, eee.), ee eeee ee eeeeeee eeeee-, eeee-, eee eeee-eeeeeeeeeee eeee eeeeee eee eeee eeeeeeeee. Me eee eeeeeee eeee eee eeee-eeeeeeee-eeee eeeee ee eeeeeeeeeeeee eeeeee eeeeeee eee eeeeeeeeeeee eeeee ee eeee-eeeeeeee-eeee eeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee M—M Meeeeeeeeee eeee Meeeeeeeeeeeeee Meee/Meeeeeeeeeeeeee Meeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 Meeeee (%) Mee
8-MeM8M8 M M 88e [‌888‌]
Me M M 88 (88) [‌888‌]
8-MM8M8 M M 88 (88) [‌888‌]
M M 88 [‌888‌]
Me Me M 88 (88) [‌888‌]
8-MM8M8 M M 88 (88) [‌888‌]
8-MeM8M8 Me M 88 (88) [‌888‌]
e-Me Me M 88 [‌888‌]
e-Me Me M 88 [‌888‌]
Me M M 88 [‌888‌]
Me M M 88 [‌888‌]
8-MeM8M8 M M 88 (88) [‌888‌]
8-MM8M8 M M 88 (88) [‌888‌]
8-eeeeeeeee M M 88 [‌888‌]
8-eeeeeeeee M M 88 [‌888‌]
Me Me M 88 [‌888‌]
8-MM8M8 M M 88 (88) [‌888‌]
Me Me M (88) [‌888‌]
Me MMe M (88) [‌888‌]
8-eeeeeeeee Me M 88 [‌888‌]
Me M M 88 [‌888‌]
Me Me M 88 [‌888‌]
8-MeM8MM8M8 M M 88 [‌888‌]
8-Mee Me M (88) [‌888‌]
Me Me Me (88) [‌888‌]
eMe Me M 88 [‌888‌]
eMe Me Me 88 [‌888‌]
Me Me M 88 [‌888‌]
M M 88 [‌888‌]
8-M8MM8M8 M M 88e [‌888‌]
MMMe8 Me M 88 (88) [‌888‌]
Me Me M 88 [‌888‌]

e Meeeee ee eeeeeeeeeee eeeeeeee eeeee ee eeeeeeeeeeeeee eeeeeee.

e Meeee Me(MMe)8 (8.8 eee%) eee M8M8M8 (8 eeeee), e 88% eeeee eee eeeeeeee.

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Me 8888, eee Mee eeeee eeeeeeeee eee eeeeeeeee(MM)-eeeeeeeee eeeee-eeeeeeeeeeeee ee eeee eeeeee (Meeeee 88).[‌888‌] Meee eeeeeeee eeee eee eeeee ee ee eeeeeeeee eeeeeeeee eeeee ee eeeeeeeeee e eeeeeee ee eeeeeeeeeeeeeeeeeee eeeeee eeee eeeee/eeeeee eeeeeeeee. Mee eeeeeeeeeeeeeee eeee/eeeeeeeeeeeeeee eeeeeeeee eeeeeeeee eeeeee ee e eeeeeeee eeeeee ee eee eeeeeee ee eeee eeeeeeeeeeeeee, eee Meeeeeeeeee, eeeeeeeee eeeeeeeeee, ee eeeee eeee ee eeeeeeee ee ee eeeeeee.

Meeeee 88 Meeeeeeee(MM)-Meeeeeeee eeeee-Meeeeeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 M8 M8 Meeeeee Meeee (%) Mee
M M M M Me M8M8M8 88 [‌888‌]
M M Me M Me M8M8M8 88 [‌888‌]
M M MMe M Me M8M8M8 88 [‌888‌]
M M M M Me M8M8M8 88 [‌888‌]
M M M M Me M8M8M8 88 [‌888‌]
M M Me M Me M8M8M8 88 [‌888‌]
M M Me M Me M8M8M8 88 [‌888‌]
M M MM8 M Me M8M8M8 88 [‌888‌]
M M MM8 M Me M8M8M8 88 [‌888‌]
M M Me M Me M8M8M8 88 [‌888‌]
Me M M M Me M8M8M8 88 [‌888‌]
MMe M M M Me M8M8M8 88 [‌888‌]
Me M M M Me M8M8M8 88 [‌888‌]
Me M M M Me M8M8M8 88 [‌888‌]
M Me M M Me M8M8M8 88 [‌888‌]
M Me M M Me M8M8M8 88 [‌888‌]
M MM8 M M Me M8M8M8 88 [‌888‌]
M MMe M M Me MMM8 88 (88)e [‌888‌]
M Me M M Me M8M8M8 88 [‌888‌]
M M Me M M M8M8M8 88 [‌888‌]
Me M M M Me M8M8M8 88 [‌888‌]
Me M Me M Me M8M8M8 88 [‌888‌]
M Me Me M Me M8M8M8 88 [‌888‌]
M Me Me M Me M8M8M8 88 [‌888‌]
M Me M M Me M8M8M8 88 [‌888‌]
M M MM8Me M Me M8M8M8 88 [‌888‌]
M M M M Me M8M8M8 88 [‌888‌]

e Meeee ee eeeeeeeeeee.

Me 8888, eee Meeeeeeee eeeee eeee eeeeeeee e eeeeeeeee-eeeeeeeee eeeeeeeee M(ee8)—M eeee eeeeeeeeeeeee ee eeeeee, eeeee ee eeee eeee eeee eeeeee eeeeeeeeeeee eeeeee (Meeeee 88).[‌888‌] Mee eeeeeeeeeeeeee eeeeeeeee M—M eeee eeeeeeeeee eee ee eeeeeeeeeeee eeee (eeeeeeeeeeeee)eeeeeee ee eee eeeeeee eee eeee-eeeeeeee eeeeeeeee(MMM) eeeeeeee eeeeeee [MeMe8(M8M)e] ee ee eeeeeeeeeee eeeeeeee; eeeeeee, eee eeee eeeeeeeeeeee eeeeeee eee eeeeeeee eeee e eeee-eeeeeee eeeeeeeee(MM) eeeeeeeeeee [Me(M8MMee)8(e-eeeeee)], eeeee eeeeee eee eeeeee eeeeeeeee M(ee8)—M eeeeeeeeeeeeee eeee eeeee eeeee ee e eeeeeeeeee eee eeeeeeee eeeeeee ee eeee 8 eee%. Meeeeee, ee eeeeeeeeeeee eeeeeee eeeeeeeeee eeeeeeeee e eeeeeeeeeee M/M eeeeeeee ee eee eeeee-eeeeeeee eee ee eeeeeeeeee ee e eeeeeeeeee M—M eeee eeeeeeeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee M(ee8)—M Meee Meeeeeeeeeeee eeee Meeeee Meeeeeeeeeee Meeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeee (%) Mee
eMe eMe M M 88 [‌888‌]
eMe eMe M MMe 88 [‌888‌]
eMe eMe M Me 88 [‌888‌]
eMe eMe M MM8 88 [‌888‌]
eMe eMe M Me 88 [‌888‌]
eMe eMe M MM8Me 88 [‌888‌]
eMe eMe M M 88 [‌888‌]
eMe eMe M Me 88 [‌888‌]
eMe eMe M Me 88 [‌888‌]
eMe eMe M M 88 [‌888‌]
eMe eMe Me M 88 [‌888‌]
eMe eMe MM8 M 88 [‌888‌]
Me Me M M 88 [‌888‌]
Me Me M M 88 [‌888‌]
(MM8)8M(MM8)8 M M 88 [‌888‌]
M M 88 [‌888‌]
(MM8)8 M M 88 [‌888‌]
(MM8)8 M M 88 [‌888‌]
eMe eMe M M 88e [‌888‌]
eMe eMe M MMe 88e [‌888‌]
eMe eMe Me M 88e [‌888‌]
Me Me M M 88e [‌888‌]
(MM8)8M(MM8)8 M M 88e [‌888‌]
(MM8)8 M M 88e [‌888‌]

e 8 eee% MeMe8(M8M)e eee eeee eeeeeee ee 8 eee% Me(M8MMee)8(e-eeeeee).

Meeeeeeeeeee, eee Meeeeeeee eeeee eeeeeeee eee eeeeeeeee-eeeeeeeee M—M eeeeeeeeeee ee eeee Meeeeee eeeeee (Meeeee 88).[‌888‌] Mee eeeeeeee eeeeeeeee eeeeeeeee eeeeeeee eeeeee eee eee eeee- eee eeee-eeeeeeeeee eeeeeeeee ee eeeee-eeeeeeeeeeee Meeeeee eeeeee 88 eeee e eeeee eeeee eeeee eeeeeeeeeee eeee eeeeeeee eeeeeeeeee. Mee eeeeeeeee eeeeeeeeee ee M—M eeee eeeeeeeeeeee ee eeee Meeeeee eeeeee eee eeee eeeeeeeeeee ee eee eeee eeeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeee 8-eeeeeeeeeeeeeeeeeeee. Meeeeeeeeeee, eee eeeeeee eeeeeee eee eeeeeeee eeeeeeeeeee eeeeeee, eeeeeeeee eeeeee eeeeeee eee e eeeeeeeeeee eeeeeeee M—M eeee eeeeeeeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee M—M Meeeeeeeeee ee Meeeeee Meeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 Meeee (%) Mee
Me Me M 88 [‌888‌]
Me Me Me 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me Me 88 [‌888‌]
Me Me Me 88 [‌888‌]
Me Me MM8 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me Me 88 [‌888‌]
Me Me M 88 [‌888‌]
Me Me MM8Me 88 [‌888‌]

Mee Mee eeeee eee eeeeeeeee eee eeeeeeeee-eeeeeeeee M—M eeee- eee eeeeeeeeeeeeeee ee eeeeee eeeeeeeeee M-eeeeeeeeeeeeeeee (Meeeee 88 eee Meeeee 88),[‌888‌] eeeee eee eeeeeee e eeeee eeeee ee 8-eeeeeeeeeeee eee 8-eeeeeeeeeeee-8,8-eeeee eeeee eeeeeeee eeeeeeeeee. Me eee eeeeee, eee eeeeeee eeeee eeee 8,8-eeeeeeee-M-eeeeeeeeeeeeeee eee eee eeeeeee eeeeeeeee eeeeeee eeeeeeeee ee eeeeeee eeeeeeeee eeeeee. M eeeeeee ee M-eeeeeeeeeeeeeeee eeee eee eeee eeee eeeeeeeeeee eeeeeeee eeee eee eeeeeeeeeeeee eeeeeeeeeeeeeeee eeeeeeee eeee 8.8 eeeeeeeeeee ee eeeeeeeee eeeeeeeeee, eee eeee eeeeee eee eeeeeeeeeeeee eeeeeeeeeeeeee eeeeeeee ee eeee ee eeeeeeeee eeeeee eeee 8 eeeeeeeeeee ee eeeeeeeee eeeeeeeeee. Me eeeeeeee, eee eeeeeeeee eeeee (eee eeeee-eeeeeeeeeee eeeeeee eeee) eeeeee eee ee eeeeeee eeeeeeee ee eee eeeeeeeee ee eeeeeeeeeeee eeee ee eeeeeeeeeeeeeeee eee eeeeeeeeeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee M—M Meeeeeeeeeeeeeeee ee 8,8-Meeeeeee-M-eeeeeeeeeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 M8 M8 Meeee (%) Mee
M M M M M 88 [‌888‌]
Me M M M M 88 [‌888‌]
Me M M M M 88 [‌888‌]
MM8 M M M M 88 [‌888‌]
Me M M M M 88 [‌888‌]
MMe M M M M 88 [‌888‌]
M M M M M 88 [‌888‌]
M Me M M M 88 [‌888‌]
M Me M M M 88 [‌888‌]
M M M M M 88 [‌888‌]
M MM8 M M M 88 [‌888‌]
M Me M M M 88 [‌888‌]
M M M M M 88 [‌888‌]
M M Me M M 88 [‌888‌]
M M M M M 88 [‌888‌]
M M MMe M M 88 [‌888‌]
M M Me M M 88 [‌888‌]
M M Me M M 88 [‌888‌]
M M M M M 88 [‌888‌]
M M MM8 M M 88 [‌888‌]
M M MM8Me M M 88 [‌888‌]
M Me M M M 88 [‌888‌]
M Me Me M M 88 [‌888‌]
Me M Me M M 88 [‌888‌]
Me M M Me M 88 [‌888‌]
M M M M (MM8)8Me 88 [‌888‌]
M M M M Me 88 [‌888‌]
M M M M Me 88 [‌888‌]
M M M M Me 88 [‌888‌]

Meeeee 88 Meeeeeeee-Meeeeeeee M—M Meeeeeeeeeeeeee ee 8,8-Meeeeeee-M-eeeeeeeeeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
M M 88 [‌888‌]
M Me 88 [‌888‌]
M M 88 [‌888‌]
M Me 88 [‌888‌]
M MM8Me 88 [‌888‌]
M Me 88 [‌888‌]
M M 88 [‌888‌]
M MM8 88 [‌888‌]
M MMe 88 [‌888‌]
Me M 88 [‌888‌]

Meeeeeee, Mee eee Meeeeeeee eeeeeeeeeeee eee eeeeeeeee-eeeeeeeee M(ee8)—M eeee eeeeeeeeeee ee eeeeee eeeeeeeeeee (Meeeee 88).[‌888‌] Meeeeeeee eeeeeeeee eeeeeeeee eeeee eee eeeeeeeee eeeeee eeeeeeeeeeeeee ee eeee eeeeeeeeee 88 eeee eeee eeeeeeeee eeeeeeee ee eeee ee eeeeeeeee eeeee- eee eeeee-eeeeeeeeeeeee eeeee eeeeeeeeee eeee eeeeeeee eeeeeeeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee M—M Meeeeeeeeee ee Meeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeee (%) Mee
Me M Me M 88 [‌888‌]
Me M Me M 88 [‌888‌]
eMe M Me M 88 [‌888‌]
Me M MMe M 88 [‌888‌]
Me M Me M 88 [‌888‌]
Me M M M 88 [‌888‌]
Me Me M M 88 [‌888‌]
Me Me M M 88 [‌888‌]
Me eMe M M 88 [‌888‌]
Me M M M 88 [‌888‌]
Me Me M M 88 [‌888‌]
Me Me M M 88 [‌888‌]
Me M M M 88 [‌888‌]
Me M M M 88 [‌888‌]
Me M M Me 88 [‌888‌]
Me M M MMe 88 [‌888‌]
Me M M M 88 [‌888‌]
Me M Me M 88 [‌888‌]
Me M Me Me 88 [‌888‌]
Me Me M Me 88 [‌888‌]
Me Me Me M 88 [‌888‌]
Me Me M Me 88 [‌888‌]

Meeeeee eeeeeeeee-eeeeeeeee eeeee-eeeeeeeeeeeee, eeeeeeeee-eeeeeeeee eeeee-eeeeeeeeeeeee eee eeeee-eeeeeeeeeeee eeee eeee eeee eeeeeeee.

Mee Meeeeeeeee eeeee eee eeeeeeeee eee eeeee-eeeeeeeeeeeeeeee ee M-eeeeeeeeeeeeeee eeee eeeeeeeeeee eeeeeee eeeee ee eee eeeeeeee ee eeeeeeee(e-eeeeee)eeeeeeeee(MM) eeeee [{MeMe8(e-eeeeee)}8], eeeeee(M) eeeeeeeeeeeeeeeeeeee, eee eeeeeeee eeeeeeeeee ee 8,8-eeeeeeeeeeeeee ee 888 °M eee 88 eeeee (Meeeee 88).[‌888‌] Meeeeeeeeeee, eee eeeeeeeeee eeeeee ee eee M-eeeeeeeeeeeeee eeeeeeee 88 eee ee eeeeeeeee eeee e eeeeeee eeeee ee eee eeeeeeee ee eeee ee eeee.

Meeeee 88 eeeee-Meeeeeeeeeeeeeee ee M-Meeeeeeeeeeeeee eeee Meeeeeee Meeee Meeeeeeee ee e Meeeeeeee(MM) Meeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 Me8 Meeee (%) Mee
M MMe MMe 8-Mee 88 [‌888‌]
M MMe MMe Me 88 [‌888‌]
M MMe MMe 8-MM8M8 88 [‌888‌]
M MMe MMe 8-MeM8M8 88 [‌888‌]
M MMe MMe 8-MM8M8 88 [‌888‌]
M MMe MMe 8-M8MM8M8 88 [‌888‌]
M MMe MMe 8-M8MM8M8 88 [‌888‌]
M MMe MMe 8-MM8M8 88 [‌888‌]
M MMe MMe 8-MeM8M8 88 [‌888‌]
M MMe MMe 8-MM8M8 88 [‌888‌]
M MMe MMe 8-eeeeeeee 88 [‌888‌]
M M MMe 8-MeM8M8 88 [‌888‌]
M M MMe Me 88 [‌888‌]
M M MMe 8-M8MM8M8 88 [‌888‌]
M M Me 8-MeM8M8 88 [‌888‌]
M M M 8-MeM8M8 88 [‌888‌]
M M M 8-MeM8M8 88 [‌888‌]
M M Me 8-MeM8M8 88 [‌888‌]
M M Me 8-MeM8M8 88 [‌888‌]
M M M 8-MeM8M8 88 [‌888‌]
M M MM8 8-MeM8M8 88 [‌888‌]
Me M M 8-MeM8M8 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

eeee-Meeee 8-Meeeeeeeeeeee Meeeeee 88; Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeeee, eeeee-eeeeee, eeeeee 88-eM eeee, e eeeeeee ee eee eeeeee eeeeeeeee (8.8 eeee), Me(M8MMee)8(e-eeeeee) (8.8–8.8 eee%), eee MeM(MMe)8 (8.8 eeeee) ee MMM/MMMM (8:8; 8.8 eM) eee eeeeeee ee 888 °M eee 88 e. Me eeeeeee eeeeeeeeeee, eee eeeeeee eee eeeeeee eeee M8M (88 eM) eee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (88 eM) eee eeeee (Me8MM8). Meeee eeeeeeeeee eee eeeeeeeeeee ee eee eeeeeeee eeeee eeeeeee eeeeeeee, eee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).

8-(Meeeeeeeeeeeeee)eeeeee Meeeeeeee 88; Meeeeee Meeeeeeee:[‌888‌]

{MeMe8(e-eeeeee)}8 (8.88 eeee, 8 eee%), MeMeM8 (8.88 eeee, 88 eee%), (MM8)8M8M8 (8.8 eeee), eee eeeeeeeee eeeeeeeee (8.8 eeee), eee ee eeeeeeee eeee (8.8 eeee) eeee eeeee ee e 88-eM eeeeeeee eeee, eeeee eee eeeeeeee eeee e eeeeeeee eeeeeee eee eee e eeeeee. Mee eeeeeeee eeee eee eeeeeeeee eee eeeeee eeee M8 eee (8 ×). (Meee: MeMeM8 ee eeeeeeee-eeeeeeeee eee eeeeeeeee eee eeeee eeeeee e M8-eeeeee eeeeeeee). Me eee eeee eee eeee eeeee 8,8-eeeeeeeeeeeeee (8.8 eM) ee eeeeeee, eee eeeee eee eeee eee eeeeeeeee eee eeeeee eeee M8 eee (8 ×). Meee, eee eeeeee eee eeeeeee eee eeeeeeeeeee e eeeee eee eee eeee ee eeeee eee eeee. Mee eeeeeee eee eeeeeee ee 888 °M eee 88 e. Meeee eeeeeee ee eeeeeee eeeeeeeeeee, eee eeeeeee eee eeeeeee eeee MM8Me8 eee eeee eeeeeeee eeeeeee Meeeee eee eeeeee eee. Mee eeeeeeee eee eeeeeeeeeeee, eee eee eeeee eeeeeee eee eeeeeeee eeeeeee e eeeeee (eeeeee eee, eeeeeee/MeMMe) ee eeee eee eeee eeeeeee.

References