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Please login or sign up for a free trial to access the full content. Catalysis by Non-heme Iron Complexes

DOI: 10.1055/sos-SD-218-00197

Hitomi, Y.; Arakawa, K.Science of Synthesis: Catalytic Transformations via C—H Activation, (20152297.

Rieske dioxygenases contain a Rieske-type [2Fe–2S] cluster and a mononuclear non-heme iron ion in a common 2-His-1-carboxylate facial triad motif.[‌37‌] Crystallographic studies indicate the formation of a side-on (hydro)peroxoiron(III) species at the active site.[‌38‌] One proposed reaction mechanism involving an oxo(hydroxo)iron(V) species is shown in Scheme 8.

Meeeee 8 Meeeeeee Meeeeeee Meeeeeeee eee Meeeeeeeeee Meeeeeeeeee[‌88‌]

Meeeeee Meeeee eeeeeeeeeeee, eeeee eee eeeeeeeeeee eee-eeee eeee eeeeeeeeee eeee eeeeeee eeeeeee(MM) eeeeeee eeeeeee ee eee(eeeeeee)eeee(M) eeeeeee ee eeeeeeee eeeee eeeeeeeeeeeee. Mee eeeeeee, eee α-eeeeeeeeeeeee-eeeeeeeee eee-eeee eeee eeeeee 8-eeeeeeeeeeeeeeeeeeeee eeeeeeeeeee eeeeeeeee eee eeeeeeeee ee (8-eeeeeeeeeeeee)eeeeeeee ee 8-(8,8-eeeeeeeeeeeeeee)eeeeeee (eeeeeeeeeeeee) eee ee eeeeeeeeeeeee eeeeee eeeeeeeee eeeeeeee ee e 8,8-eeeeeee (MMM) eeeee (Meeeee 8).[‌88‌] Meeeee-eeeeeeeee eeeeeeee eeeee eeee eeeeeeeeeeee eeeeeeee eeeeeeeeeeeee ee eeeeeeeeeeeee, eeeeeeee, eee eeeeeeeeee eeeee eee eeeeeeee eeeeeeeeeeeeeeeeeee eee eeeeeeee (Meeeee 88).[‌88‌]

Meeeee 8 Meeeeeeeeeeee Meeeeeeee ee e α-Meeeeeeeeeeee-Meeeeeeee Mee-eeee Meee Meeeee[‌88‌]

Meeeee 88 Meeeeeee Meeeeeeee ee Meeeeeee Meeee Meee Meeeeeeeeeee[‌88‌]

Meeeeee eeeeeeeeeeeeee eeeeeeee eee MMMM- eee eeeeeeee-eeeeeeeee eeeeeeeeee ee eeeeeee eeee e-eeeeee.[‌88‌] Meeeeee eeeeeeeeeeeeee eeeeee ee e eeeeee ee eeeeeee eeeeee eeeeeeeeeeee eeee eeeeeeee eeeeeee eeeeeeeeeeeee, eeeeee eeeeeeeeeeee, eee eeeeee eeeeeeeeee.[‌88‌] Mee eeeeeeeee eeeeeee ee eeeeeee ee eeeeeeeee eeeeee eeeeeeeeeeee ee eeeeeee (Meeeee 88): eeeeeee 8-eeeeeeeeeeeee eeee Meeeeeeeeeee eeeeeee M8,[‌88‌] eeeeeee 8-eeeeeeeeeeeee eeee Meeeeeeeeee eeeeeeeee MMM8,[‌88‌] eee eeeeeee 8-eeeeeeeeeeeee eeee Meeeeeeeeee eeeeeeeee MM8[‌88‌] eeeee e-, e-, eee e-eeeeee, eeeeeeeeeeee.

Meeeee 88 Meeeeeeee ee Meeeeee Meeeeeeee ee Meeeeeeee Meeeee Meeeeeeeeeee[‌88‌]

Meee-eeeeeeeee eeeeeeeee eeeeeee eeeeeeeee eeeeeeee ee eeeeeeee eeeeeeee, eeee ee Meeeeeʼe eeeeeeeee,[‌88‌‌88‌] eeeeee ee eee eeeeee eee eeee eeeeeeeeeeeee.[‌88‌] Meee eeeeeeeeeeeee eeee-eeeee eeeeeee eeeeeeee eee eeeeeeeee ee eeeeeee ee eeeeee eeee eeee eeeeeeeeeeeee (ee ee 88% eeeee ee eeeeeee), eee eee eeeeeee eeeeeeeeeee (ee ee 88%).[‌88‌‌88‌] Me 8888, Meeeeee eee Meeeeee eeeeeeee e eeeeee eee eeeeee eeee-eeeee eeeeeeee eee eee eeeeeeee eeeeeeeee ee eeeeeee ee eeeeee eeee eeeeeeee eeeeeeee.[‌88‌] Meee eeeeeeee eeee eee eee ee e eeeeeeee eeeeeeee eeeeee [eeeee/eeeeeeeeeeee (8:8)] eeeeeeeeee eeeeeeee eee eeeeeeeeeee ee eee eeeeeeee. Me eeeeeeee, eee eee ee 8-eeeeeee-8-eeeeeeeeeeeeee 8-eeeee ee eeeeeeeeee eeeeeee ee eee eeee eeeeeeeeeee (88%) (Meeeee 88). Meeee eee eeee eeeeeeeeee, eeeeeee ee eeeeeeeee eeee e eeeeeee ee e- eee e-eeeeee (eeeee 88%), eee eeeeee eeeeeee, eeeeeeeeeeee, eee eeeeeee eeee (eeeee 88%).

Meeeee 88 Meeeeeee Meeeeeeee ee Meeeeee ee Meeeee eeee Meeeeeee Meeeeeee[‌88‌]

Mee eee ee-eeeeeee eeee eeeeeeee eee eeeeeeeeeeeeee eeeeeeee eeeeeeeeeeeee ee eee ee eee eeeeee eeeeeeeeeeee eeee eeeeeeee ee e eeeeeeeeeeeeeeeeee(MM) eeeeeee eeee e eeeeeeeeee eeeeeeeee eeeeeeeee(8,8-eeeeeeeeeeeeeee-8-ee)eeeeee eeeeee eeee eeeeeeee (Meeeee 88).[‌88‌] Meeeeee-eeeeeeee eeeeeee eeee eeee 88M8 ee eeeeeeeeeeee eeee eee eeeeeeeeeeee eeeeee eeee ee eee eeeeee eee eeeeeee eeee. Meee, eeee ee eee eeeee eeeeeee ee eeeeeeeee eee eeeeeeee ee α-eeeeeeeeeeeee-eeeeeeeee eee-eeee eeee eeeeeee eee eeeeeeee eeeeeeeeee. Mee Mee eeeee eeee eeee eeeeeeee e eeeeeee eeeeeeeeeeeeee eeeee eeeeeeeeeeeee eeeee e eeeeeeeeeee eee-eeee eeee eeeeeee eeeeeeeee ee e eeeeeeeeeeee eeeeeeee eeeeee eeee e eeeeee eeeee.[‌88‌] Me eee eeeeeeeee eeee eee eeeeeeee ee eee eee-eeee eeee(MM) eeeeeee eeee eeee-eeeeeeeeeeeeeeeeee eeeeeee ee eee eeeeeeeee ee ee eeeeeee(MM) eeeeeee eee M—M eeee eeeeeeeee ee eee eeeeeeee eeeeeeeeeeeeeee(MMM) eeeeeee (Meeeee 88).

Meeeee 88 Meee-Meeeeeeeeeeee Meeee ee Meeeeeeeee Meee Meeeeeeee[‌88‌,‌88‌]

Me eeeeeeeee eeeee, eeeeeeeeeeeeee eeeee eeeeeeeeeeeeee eeeeee eeeeeeeeee eeeee eeeeeeeee eeee eeee eeeeeeee.[‌88‌‌88‌] Meeee eeeeeeeee eee ee eeeeeee eeeeeeeee eeeeeee; eeeeeee, eeeeeeeee eeeee-eeeeeeeeeeeee ee eeeeee eee eeee eeeeeeee eeeee e eeeeeee ee eeeeeeeeeee eeeeeeeeeeeee ee e eeeeeeeee eeeee. Me 8888, Meeeeeee eee ee-eeeeeee eeeeeeee eee eeeee-eeeeeeeeeeeee ee 8-eeee-eeeeeeeeeee ee eee-eeee eeee eeeeeeeee eee eeeeeeee ee e eeeeeeeeee eeeee eeeeeeee eee eeeeee-eeeeeeeee eeeeeeee eeeeeeeeeee (Meeeee 88).[‌88‌] Meeeeeeeeeeee eeeeeeee ee 88 °M eeeee 8 eeeeeeeeee ee eeeeeeee ee eeeeeeee ee ee eeeeeeeeeeee eeeeeeee ee eeee(MMM) eeeeeeee eee eeeeeeee ee 8-eeee-eeeeeeeeeee, e eeeeeeee, eee e eeeeeeeeeeee. 8-eeee-Meeeeeeeeeeee eee eeeeeeee ee eee eeee eeeeeeeeee eeeeeee. Mee eeeeeee eeeee eee eeeeeeee eeee eeeeeeeeeeeeeeeeeee eee 8,8-ee-eeee-eeeeeeeeeeeeeeeee.

Meeeee 88 Meeeeeeeee eeeee-Meeeeeeeeeeee ee 8-eeee-Meeeeeeeeee Meeeeeeee ee e Mee-eeee Meee Meeeeee[‌88‌]

Me 8888, Meeee-Meeeeee, Mee, eee ee-eeeeeee eeeeeeee eee eeeee-eeeeeeeeeeeee ee e eeee eeeeeee ee eeeeeeeeeee eeeeeee eeeee ee eeeeeeeee eeeeeeeeeeeeee eeeeeee ee e eeeeeeeeeee eeee(MM) eeeeeee [MeMM(eeeee)(MMMe)8](MeM8)8 (88) ee [MeMM(eee)(MMMe)8](MMe)8 (88) [eeeee = M,M′-eeeeeeee-M,M′-eee(8-eeeeeeeeeeeee)eeeeeeee-8,8-eeeeeee, eee = eeee(8-eeeeeeeeeeeee)eeeee] eeee eeeeeeee eeeeeeee ee eeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meee-Meeeeeee eeeee- eee eeee-Meeeeeeeeeeee ee Meeeeee Meeee eeee Meeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeeeeee Meeeee (%) ee 88 Meeeee (%) ee 88 Mee
MMe M M 88 88 [‌88‌]
MMe M M 88 88 [‌88‌]
M MMe M 88 88 [‌88‌]
M MMe M 88 88 [‌88‌]
M M MMe 88 88 [‌88‌]
M M MMe 88 e e [‌88‌]
Me M M 88 e 88 [‌88‌]
Me M M 88 88 [‌88‌]
M Me M 88 >88 [‌88‌]
M Me M 88 88 [‌88‌]
M M Me 88 e 88 [‌88‌]
M M Me 88 88 [‌88‌]
M M M 88 88 [‌88‌]
M M M 88 88 88 [‌88‌]
Me M M 88 e 88 [‌88‌]
Me M M 88 88 [‌88‌]
M Me M 88 88 [‌88‌]
M Me M 88 88 [‌88‌]
M M Me 88 e 88 [‌88‌]
M M Me 88 88 [‌88‌]
MM8 M M 88 88 88 [‌88‌]
MM8 M M 88 88 [‌88‌]
M MM8 M 88 88 [‌88‌]
M MM8 M 88 e e [‌88‌]
M M MM8 88 88 [‌88‌]
M M MM8 88 e e [‌88‌]

e Meeee ee MM/eee eeeeeeee.

e Meeee ee MM eeeeeeee.

e Me eeeeeeee.

e Me ee eeeeeeeeee ee eeeeeeeeeeeee eeeeeeee eee eeeee ee eeee eeeeeee eeee MM/eee eeee.

Meeeeeeeeee eeeeeeeeee eeeeeeeeee eeeeeee eeeeeeeee eeeeee eeee eeee eeeeeeee. Me 8888, Mee eee ee-eeeeeee eeeeeeee eee eeeee eeeeeee ee e eeeeeeeeee eee-eeeeeeeeeeeeeee ee eeeeeeeeeee eeee eeeeeeee eeeeeeee eeeee e eee-eeee eeee(MM) eeeeeee [MeMM(eee)(MMMe)8]8+ [eee = eeee(8-eeeeeeeeeeeee)eeeee] (Meeeee 88).[‌88‌] eee-8,8-Meeeeee-8,8-eeeeeeeeeeeeeeeeeeee eee eeeeeeee ee eee eeee eeeeeee (88% eeeee ee eeeeeeee eeeeeeee), eeeeeeee eeee eeeeeee eeeee eeeeeeee, eeeeee 8-eeeeeeee (8%), 8-eeeeeeee (8%), eee eeeeeee-8,8-eeeeeee (8%).

Meeeee 88 Meeeeeeeee eee-Meeeeeeeeeeeeee ee Meeeeeeeeee Meeeeeeee ee e Mee-eeee Meee Meeeeee[‌88‌]

Mee eeeeeeeee eeeeeeeee ee eeeeee ee eeeeeeee ee ee eeeeeeeeeee eeeeeeee ee eee eeeeeeee eeeeeeee.[‌88‌] Meeee eee eeeeeeeeeeee eeeeeeee eeeeeeee, 8,8,8-eeeeeeeeeeeeee-8,8-eeeeeee (MMMM) ee eeeeeeee ee ee eeeeeeeeeeee eee eee eeeeeeeee ee eeeeeee M (α-eeeeeeeeee),[‌88‌,‌88‌] eee ee eeeeeeee ee eee eeeeeeeee eeeee eeeeeeeee ee 8,8,8-eeeeeeeeeeeeeee. Me eeee, eeeeeee eeeeeeeee eeee eeee eeeeeeeeeee eee eee eeeeee eeeeeeeee ee 8,8,8-eeeeeeeeeeeeeee ee 8,8,8-eeeeeeeeeeeeee-8,8-eeeeeee, eeeeee eee ee eeee eee ee eeeeeeeeee eeeeeeeee.[‌88‌‌88‌]

Me 8888, Meeeee eee ee-eeeeeee eeeeeeee eee eeeeeeeee ee 8,8,8-eeeeeeeeeeeeeee ee 8,8,8-eeeeeeeeeeeeee-8,8-eeeeeee eeee eeeeeeee eeeeeeee ee eee eeeeeeee ee eeee(MMM) eeeeeeee eeeeeeeeeee, eeeeeeee-8,8-eeeeeeeeeeee eeee, eee eeeeeee eeeeeeeeeeee.[‌88‌] Mee eeee eeeee eee eeeeeeeeeee eeee eeeeeeee eeee M-eeeeeeeeeeeeeeee eee eeee. Meeeee eee ee-eeeeeee eeeeeee eeee eeeeee eee eee eeeeee eeeeeeeeee ee eeeeeee eeeeee eeee eeeeeeee (Meeee 8).

Meeee 8 Meeeeeeee Meeeeeeee ee Meeeee ee eee Meeeeeeeeeeee Meeeeeee[‌88‌]

Meeee Meeeeeeee eee% ee Meeeeeee Meeee Meeeeee Meeeeeeeeee (%) Meeeeeeeeeee,e (%) Mee
 8 8.8 >88 88 (88)e [‌88‌]
 8 8.8 88 88 [‌88‌]
 8 8.8 >88 88 [‌88‌]
 8 8.8 >88 88 [‌88‌]
 8 8.8 >88 88 [‌88‌]
 8 8.8 >88 88 [‌88‌]
 8 8.8 88 88 [‌88‌]
 8 8.88 >88 88e [‌88‌]
 8 8.88 >88 88e [‌88‌]
88 8.88 >88 88 [‌88‌]
88 8.88 >88 88 [‌88‌]

e Meeeeeeeee eee eeeee eeee eeeeeeeeee ee MM eeeeeeee eeeee 8.8 e, eeeee eeeeeeee (8.88 eeee) ee eee eeeeeeee eeeeeeee.

e Meeeeeeeeee eeeeee ee eee eeeeeeeeeeeeeeee ee eeeeeee eeee eeeee.

e Meeeeeee eeeee.

e 8-Meeeeeeeeeeee-8,8-eeeeeee: 88% eeeee, 8-eeeeeeeeeeeee-8,8-eeeeeee: 88% eeeee.

e 8,8-Meeeeeeeeeeeeee-8,8-eeeeeee: 88% eeeee; 8,8-eeeeeeeeeeeeeee-8,8-eeeeeee: 8% eeeee.

Meeee, Meeeeee, eee ee-eeeeeee eeee eeeeeeee eee eeeeeeeeee eeeeeeeee ee eeeeeeee eeeeeeeeeee.[‌88‌] Meeeeeeee ee Meeeeeeee (88) [MMM; (M)-8-eeeeee-8-(eeeeeeeeeeeeeeeeee)-8-(eeeeeeeeeeeeeee)-8,8-eeeeeee-8M-eeeee[e][8,8]eeeeee-8-eee], e eee-eeeeeeeeee eeeeeee eeeeeeeeeeeee eeeeeeeee eeeeeeeeeeee ee e eeeee-eeee eeeeeeeee eeeeeee eeeee eeeeeeeeeeeeeeee eeeee, ee eeeeeeee ee eee eeeeeeee eeee ee eee eeeeeeee eeeeeee 8-eeeeee-8-(eeeeeeeeeeeeeeeeee)-8-eeeeeee-8-(eeeeeeeeeeeeeee)-8M-eeeee[e][8,8]eeeeee-8(8M)-eee (88) eeeee eeee eeeeeee 88 ee e eeeeeeee, eeeeee eeee ee e eeeeeeeeee, eee eeeeeeee eeeeeeee ee eee eeeeeee (Meeeee 88).

Meeeee 88 Meee-Meeeeeeee Meeeeeeee ee Meeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee, e.e. 88; Meeeeee Meeeeeeee:[‌88‌]

MeMM8•8M8M (8.8 eeee), MMM (8.8 eeee), eee 8-eeeeeee-8-eeeeeeeeeeeeee 8-eeeee eeee eeeeeeeee ee M8M (888 eM), eee eee eeeeeee eee eeeeeee eee 8 e ee 88 °M. Mee eeeeeeeee eeee eee eeeee ee e eeeeeee ee MeMM (888 eM) eee eeeeeee (88 eM, 888 eeee) (MMMMMMM: eeeeeeeeee). Mee eeeeeeeee eeeeeeee eeeeee eee eeeeeee ee 888 eee ee 88 °M, eee 88% ee M8M8 (88 eeee) eee eeeeeeeeeeeee eeeee eeee e eeeeeeeeeee eeee eeee 8 e. Me eee eee ee eee eeeeeeee, eee M8M8 eeeeeeeeeeeee ee eee eeeeeee eeeee eee eeeeeeeeee ee eeeeeeeee eeee MMeM8, eee eee eeeeeeeeeeeee ee eeeeeeeee eeeeeeee ee eee eeeeeee eee eeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee. M8M8 eee eeeeeee eeeeeeeeee eeee 88 eee 8.8%, eeeeeeeeeeee, eeee eeeeeeeeeeeee ee eeeeee ee 88 eee 88% eeeee ee M8M8 eee eeeeeee, eeeeeeeeeeee. Mee eeeee eeeee ee eeeeeeee ee ee eeeeeee: eeeeee/eeeeeeeeeeee/eeeeeeee/eeeee-8,8-eeeeeee/eeeeeeee/eeee = 88.8:8.8:8.8:8.8:8.8:8.8.

8,8,8-Meeeeeeeeeeeee-8,8-eeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

Me e 88-eM eeeee, eee eeeeeeee (MeMe8•8M8M/eeeeeeee-8,8-eeeeeeeeeeee eeee/MeMMMe 8:8:8.8; 8.8 eee%) ee 8-eeeeeeeeeee-8-ee (8 eM) eee eeeeeee ee ee eee 88 eee ee ee eeeeeeeeee eeee. Meeeeeeee (8.8 eeee) eee eeeeeeee (MM eeeeeeee eeeeeeee, 888 µM) eeee eeeee ee eee eeeeeee ee 8 °M. M eeee ee 88% M8M8 (8 eeeee) ee 8-eeeeeeeeeee-8-ee (888 µM) eee eeeee eeee e eeeeee ee 8 e eeeee e eeeeeee eeee. Meeeeeee eeee eeeee eeee eee eeeeeee 88 eee eeeee eee eeeeeeee eee eeeeeeeee ee MM eeeeeeee eee eeeeeeeeeeeee ee eeeee eee eeeeeeeeee.

8-Meeeeeeeeeeee-8,8-eeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

Me e 88-eM eeeee, eee eeeeeeee (MeMe8•8M8M/eeeeeeee-8,8-eeeeeeeeeeee eeee/MeMMMe, 8:8:8.8; 8.88 eee%) ee 8-eeeeeeeeeee-8-ee (88.8 eM) eee eeeeeee ee ee eee 88 eee ee ee eeeeeeeeee eeee. Meeeeeeee (8.8 eeee) eee eeeeeeee (MM eeeeeeee eeeeeeee, 888 µM) eeee eeeee ee eee eeeeeee (8 eM) ee ee. M eeee ee 88% M8M8 (8.8 eeeee) ee 8-eeeeeeeeeee-8-ee (888 eM) eee eeeee eeeeeeee. Meeee 88 eee, eee eeeeeeeee eeeeeeee eeee eee M8M8 (8.8 eeeee) ee 8-eeeeeeeeeee-8-ee (888 µM) eeee eeeee. Meeeeeee eeee eeeee eeee eee eeeeeee 8 e eeeee eee eeee eeeeeeee eee eeeeeeeee ee MM eeeeeeee eee eeeeeeeeeeeee ee eeeee eee eeeeeeeeee.

8-Meeeee-8-(eeeeeeeeeeeeeeeeee)-8-eeeeeee-8-(eeeeeeeeeeeeeee)-8M-eeeee[e][8,8]eeeeee-8(8M)-eee (88):[‌88‌]

MeMM (88 µM, 8.8 eeee, 8 eeeee) eee eeeee ee e eeee ee (M)-8-eeeeee-8-(eeeeeeeeeeeeeeeeee)-8-(eeeeeeeeeeeeeee)-8,8-eeeeeee-8M-eeeee[e][8,8]eeeeee-8-eee (88; 888 ee, 888 µeee) eee eeeeeeee 88 (88 eee%) ee MeMM/MeMMe (8:8; 8 eM). Mee eeee eee eeeeeee eee 88 ee% M8M8 (88 µM, 888 µeee, 8.88 eeeee) eee eeeee ee ee. Mee eeeee eeeeeee eee eeeeeee ee 88 °M eee 8 e eee eee eeeeeeee eeeeeeee eee eeeeeeeee ee MMMM. Mee eeeeeee eee eeee eeeeeee eeee eee. ee MeMMM8 (8 eM) eee MeMMe (8 eM) eee eee eeeeeee eeeeeeee eee eeeeee eeeeeeeeeeee eeee ee MeMMM8, M8M, eee eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8 ee MM8Me8/MeMM 88:8), ee eeee eee eeeee eeeeeeee; eeeee: 88 ee (8.8%). Mee eeeeeeeee eeeeeeee eeeeeeee 88 eee eeeeeeeee eeeeeeeeeeeeee (88 ee).