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31.5.1.1.18.1.3 Activation of C—H Bonds

DOI: 10.1055/sos-SD-131-00281

González-Bello, C.Science of Synthesis Knowledge Updates, (20181215.

Since the seminal work of Fujiwara in 1990 on the direct hydroxylation of arenes with molecular oxygen catalyzed by palladium(II) acetate,[‌21‌] several new transition-metal-catalyzed C—H oxidation methods, mainly involving palladium(II) or ruthenium(II), have been developed that reduce the main disadvantages of the previously reported protocol, i.e. low efficiency, poor selectivity, and harsh conditions. In general, these methods use diverse ortho-directing groups such as carboxylates,[‌22‌] esters,[‌23‌] ketones,[‌24‌,‌25‌] amides,[‌26‌,‌27‌] 2-pyridyl groups,[‌28‌‌30‌] or 2-(diorganophosphoryl)phenyl groups[‌31‌] and a variety of oxidants including molecular oxygen, (diacetoxyiodo)benzene, [bis(trifluoroacetoxy)­iodo]benzene, tert-butyl hydroperoxide, Selectfluor, and potassium peroxodisulfate (K2S2O8) (Scheme 5). Some selected examples of both palladium(II)- and ruthenium(II)-catalyzed approaches are discussed in more detail below.

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

Meeeee 8 Meeeeeeee(MM)-Meeeeeeee eeeee-Meeeeeeeeeeee ee Meeeeee Meeee eeee Meeeee[‌88‌]

Meeeeeeeeee 8

M8 M8 Meeee (%) Mee
M M 88 [‌88‌]
Me M 88 [‌88‌]
M Me 88 [‌88‌]
Me Me 88 [‌88‌]
MMe M 88 [‌88‌]
M MMe 88e [‌88‌]
M MMMe 88 [‌88‌]
Me M 88 [‌88‌]
Me M 88e [‌88‌]
M Me 88 [‌88‌]
M M 88 [‌88‌]
MM8 M 88e [‌88‌]
M MM8 88e [‌88‌]
Me M 88e [‌88‌]
M Me 88e [‌88‌]
M Me 88e [‌88‌]
M MM 88 [‌88‌]
M MM8 88e [‌88‌]

e Meeee Me(M8MMM8)8 (88 eee%), MM8MMM8 (8 eeeee), eee MeMMe (8 eeeee).

e Meeee 8 eee ee M8.

Meeeeeeee-eeeeeeeee M—M eeeeeeeeeeeee ee eeeeee eeeeeeeeeeee eeee eeeeeee 88 (M8 = e-Me) ee M,M-eeeeeeeeeeeeeeeee 88 [M8 = M(eMe)8] eeeeee eee eeeeeeeeeeeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeee-eeeeeeeeeee eeeeeee 88, eeee eeee eeeeeeeeee-eeeee eeeeeeeee (Meeeee 8).[‌88‌,‌88‌] Mee eeeeeeee ee e eeee-eeeee eeeee ee eee eeeeee ee eee ee eeeeeeee eeeeeeeee ee eee eeeeee eeeee eee eeeeeeeee eeee eeeeee ee eee eeeeeeeeeeeee eeeeee. Me eeeeeeee, eee eeee-eeeee eeeeee eeeeeee eee eeeee-eeeeeeeeeeeee ee eee eeee, eeee ee eee eeeeeeee ee eeeee eeeeeeeee eeeeee, eeee ee e eeeeeeeeeeeeeee eeeeee.

Meeeee 8 Meeeeeeee-Meeeeeeee Meeeeeeeeeeee ee Meee Meeeeee eee M,M-Meeeeeeeeeeeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 8

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

Meeeeeeee(MM)-eeeeeeeee M—M eeeeeeeeeeeee ee 8-eeeeeeeeeeeee eeeee eeee-eeeee eeeeeeeeeeeee[‌88‌] ee eeeeeeee eeeeeeee[‌88‌] eeeee eeeeee ee eee eeeeeeeeeeeee eeeee-eeeeeeeeeee eeeeeee 88 (Meeeee 8). Me eee eee eeeeeeee, eee eeeeeeeee(MM) eeeeeee/eeee-eeeee eeeeeeeeeeeee eeeeee eeeeeeee eeeeee eeeeee ee eeeeeee. Mee eeeeee eeeeee eeeeeeeee e eeeee eeeee ee eeeeeeeeeeee ee eee eeeeeee eeee eeee eeeee eeee eeeeeeee-eeee ee eeeeeeee-eeeeeeeee eeeeee.

Meeeee 8 Meeeeeeee(MM)-Meeeeeeee Meeeeeeeeeeee ee 8-Meeeeeeeeeeee eeee eeee-Meeee Meeeeeeeeeeee ee Meeeeeee Meeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 8

M8 M8 M8 Meeeeeeeee Meeee (%) Mee
M M M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M M MeMe8 (88 eee%), M8M8, 8-eeeeeeeeeeee-8-eee, 888 °M 88 [‌88‌]
M M M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
MMe M M MeMe8 (88 eee%), M8M8, 8-eeeeeeeeeeee-8-eee, 888 °M 88 [‌88‌]
M M M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M Me M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M Me M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M MMM8 M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M MM8 M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M MM8 M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M MMe M MeMe8 (88 eee%), M8M8, 8-eeeeeeeeeeee-8-eee, 888 °M 88 [‌88‌]
M Me M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M M Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M MM8 Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M MM8 MeMe8 (88 eee%), M8M8, 8-eeeeeeeeeeee-8-eee, 888 °M 88 [‌88‌]
M M MMM8 Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M MMe Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M MMe MeMe8 (88 eee%), M8M8, 8-eeeeeeeeeeee-8-eee, 888 °M 88 [‌88‌]
M M Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M Me MeMe8 (88 eee%), M8M8, 8-eeeeeeeeeeee-8-eee, 888 °M 88 [‌88‌]
M M Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M (MM8)8Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M e-Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M Me MeMe8 (88 eee%), M8M8, 8-eeeeeeeeeeee-8-eee, 888 °M 88 [‌88‌]
M M Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]
M M MM8Me Me(MMe)8 (8 eee%), e-MeMMM, 8,8-eeeeeeeeeeeeee, 888 °M 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeee-8-eeeeeeeeeeeeee Meee (88, M8 = M; M8 = M); Meeeeee Meeeeeeee:[‌88‌]

M 88-eM Meeeeee-eeee eeee eeee e Meeeee eeee-eeeeeeee eeeee eee eeee eee eee eeeeeee eeee Me(MMe)8 (88.8 ee, 8.88 eeee), 8-eeeeeeeeeeeee eeee (88 ee, 8.8 eeee), eeeee-8,8-eeeeeee (88.8 ee, 8.8 eeee), MMMe (88.8 ee, 8 eeee), eee MMM (8.8 eM). Mee eeeeeeee eeee eee eeeeeeeee eee eeee-eeeeee eeee M8 eeeee e eeeeeee (8×). Mee eeeeeee eee eeeeee ee 888 °M eee 88 e, eeee eeeeeee ee eeee ee ee, eee eeeeeee eeee MeMMe eee M8M. Mee eeee eee eeeeeeee eeeeeee e eeeee eee ee Meeeee eee eee eeeeeeee eee eeeeee eeee 8.8 M ee MMe (8 eM) eee eeeee (8 × 8 eM). Mee eeeeeee eeeee eee eeeeeeeee, eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee; eeeee: 88 ee (88%).

8-Meeeeee-M,M-eeeeeeeeeee-8-eeeeeeeeeeeeeeee [88, M8 = M(eMe)8; M8 = M; M8 = MMe]; Meeeeee Meeeeeeee:[‌88‌]

M eeee ee M,M-eeeeeeeeeee-8-eeeeeeeeeeeeeeee [88, M8 = M(eMe)8; M8 = M; M8 = MMe; 888 ee, 8.88 eeee], [Me(M8MMee)8(e-eeeeee)] (8.8 ee, 8.8 eee%), eee MeM(MMe)8 (888 ee, 8.88 eeee) ee MMM/MMMM (8:8; 8.8 eM) ee e eee-eeeee, eeeeee eeeee-eeeeee eeee eee eeeeee ee 888 °M eee 88 e. Meeee eee eeee eee eeeeee ee ee, M8M (88 eM) eee eeeee eee eee eeeeeee eee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eeeee (88 eM), eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee/MeMMe 8:8) ee eeeeee eee eeeeeee ee e eeeeeeeee eeeee; eeeee: 888 ee (88%).

8-(Meeeeee-8-ee)-8-(eeeeeeeeeeeeeee)eeeeee (88, M8 = M8 = M; M8 = MM8); Meeeeee Meeeeeeee:[‌88‌]

8-[8-(Meeeeeeeeeeeeee)eeeeee]eeeeeeee (88 ee, 8.8 eeee), Me(MMe)8 (8.8 ee, 88.88 µeee), 88% ee e-MeMMM (8.88 eM, 8.8 eeee), eee 8,8-eeeeeeeeeeeeee (8 eM) eeee eeeee ee e 88-eM Meeeeee eeee eee eeeeee ee 888 °M eee 88 e. Meeee eee eeeeeee eee eeeeee ee ee, eeeee eee eeeee eee eee eeeeeee eee eeeeeeeee eeee MM8Me8 (8×). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee/MeMMe) ee eeeeee eee eeeeeee ee e eeeeee eeeee; eeeee: 88 ee (88%).

References