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Please login to access the full content or check if you have access via Variation 1: Via Lithiation and Reaction with Electrophiles

DOI: 10.1055/sos-SD-002-00214

Kündig, E. P.; Pache, S. H.Science of Synthesis, (20032166.

Coordination of an arene to the electrophilic tricarbonylchromium fragment lowers the pKa of ring protons by ca. 6 pKa units compared to the free arene.[‌93‌,‌94‌] The first metalation of an arene chromium complex was reported in 1972,[‌95‌] and since then this reaction has seen extensive development and has been the subject of several reviews.[‌96‌‌98‌]

Meeeeeeeeeeee ee eeeeeeee eeeee ee eee eeeeeeeeeeeeeee eeee ee eeeeeee eeeeee (eeeeeee eeeeeeeeeeeeeeee, eeeeeee 8,8,8,8-eeeeeeeeeeeeeeeeeeeee) eeeee [Me(MM)8(Me8Me)] eeeeeeeee eeee eee eeeeeee eeeeeee ee eeee eeee eeeeeeeeeeeee. Meeeeeeee ee eee eeeeee ee eee eeeeeee eee eee eeeeeee, eeeeeeeeeeee eeeeeeee eeeeee eeeee ee eeeeeeeeeeeee ee ee eeeeeeee (eee Meeeeee Meeeeeeeeeeee, eeeeee eeee eeeee eeee, [Me(MM)8(Me8Me)] eeeeeeeee eee eeeeeeeeee eee eeeeeeeeeeeee eeeeeeee ee [Me(MM)8(Me8M)] (M=Me, M) eeeeeeeee.[‌88‌] Meeeee eeeeeeeeee eee ee e eeeeeee ee (eeeeeee)eeeeeeeeeeeeeeeeeee(8) (8, M=Me; M8=MMe) eee ee eeeeeeeeeee(eeeeeeeee)eeeeeeee(8) (88) (Meeeee 8).[‌888‌] Meeeeeeee ee eeeeeeeeeeeee eeeeeeeee eeeee eeee eee eeeeeeeeeeeeeeee. Meeeeeee eeeeeeeeeeeee ee eeeeeee eeeee eeeeeeeeeeeee eeeeeeeeee (eeeeeeeee eeee-eeeeeeee, eeeeeeee eeeeeeeee, 88°M),[‌888‌] eee eeeee eeeeeee eeeeeeeeee (eeeeeeeeeeee, eeeeeeeeeeeeeee, 88°M), eeeeeeeeeeeee eeeee eeeee eeeeeeeeeeeeee, eeeeee eeeeeeeee eee eeeeeeeeeee, ee eee eeee. Meee, eeeeeeeeeee(eeee­eee)eeeeeeee(8) eeeeee eeee eeeeeeeeeeee ee 88°M ee eee eeeeeeee eeee (88%) ee eeee ee ee eeee eeeeeeeee: 8% eeeee eee 88% eeee eeee eee eeee.[‌888‌] Meeeeeee ee eeeeeeeeeeeeeeee ee eeeeeeeeeeeee eeeeeeeee eeeee eeeeeee eeeeeeeeee eee eeeee ee Meeeee 8. Meeee eeeeeeeeeeee eeeeeee eeeee eeeee eeeeeeeeeeee. Meeeeeeeee, e eeeeee ee eeeeeeeeee eeeeee eeeeee eeeeeeeeee ee eee eeeee eeeeeeee: M, Me, MMe, MMMM, MM(M)MM88, MMe8, MMMMe-Me, MM(MMe)8, MM8MMe, MM8MMe8, MMM8. Mee eeeee eeeeeeeee eeeeeee eeeeee eeee eeee eeeee ee eeeeeeeeeee eeeeee eee eeeeeeeee ee eee eeeee: M > MMMMe-Me > MMe MM8MMe8 > MM8MMe (e.e., eee 88).[‌88‌] Meeeeeeeeeee eeee eeeeeeeeee eeeeee eeee MMMMM [(e/e) 8:8] eee eeee MMe(MMMMM) [(e/e) 88:8] eee eeee eee eeee eeeeeeeeee ee eee eeeeeeeee eeeeeeeeeeee ee eee Me(MM)8 eeeeee ee eee eeeeeeeeeee, eeee eeeeeeee eeeeeeeee ee e MMeM eeeeeeee ee e MeMM eeee.[‌888‌] Mee eeeeeeeeeeeeeeee eeeeeee 8 (e=8) ee eeeeeeeee eeeeeeeeeee ee eee eeeeee eeeee ee eee eeee eeeeeeee.[‌888‌,‌888‌] Meeeeeeeee eeee eeee ee eee eeeeeeeeeeeeeeeee eeeeeee ee eeeeeeeeee eeeeeeeeeeeee ee eee β-eeeeeeee [eeeeeeeeeee(eeeeee)eeeeeeee(8) (8, e=8): (α/β) 8:8 (eeee eeeeeeeeeeee); 8:88 (eeee eeeeeee 8,8,8,8-eeeeeeeeeeeeeeeeeeeee)].[‌888‌] Mee eeeeeeeee ee eee eeee ee eee eeee ee eeee eeeeeeee ee eee eeeeeeeeeeeee ee eee eeeeeeeeeee eeeeeee 88. Meeeeee 8,8,8,8-eeeeeeeeeeeeeeeeeeeee eeeeeee eeeeeeeeeee MM8, eeeee eeeeeeeeeeee eeeee, eeeee eeeeeeee eeee eeeeeeeeeeeee, e 8:8 eeeeeee ee M8/M8 eeeeeeeeeee eeeeeeee.[‌88‌‌88‌] Meee eeeeeee 88, eeeeeeeeeeeee ee eeeeeee eeeeeeeeeeeeeeee eee eeee eeeee ee ee eeeeeeeeee.[‌888‌] Meeeeeeeeeeee ee M-eeeeeeeee eeeeee eeeeeeeee 88 ee eeeeeeee ee eee 8-, 8-, ee 8-eeeeeeee, eeeeeeeee ee eee M-eeeeeeeeee eeeee eee eee eeeeeeeeeee ee M8.[‌888‌] Meee ee ee eeeeeeeee eeeeeeeeeeee eeeee eee 8-eeeeeeee ee eeeeeee ee eee eeeeeee eeeeeeeeee.

Meeeee 8 Meeeeeeeee eee Meeeeeee eeee Meeeeeeeeeeee[‌88‌,‌88‌‌88‌,‌88‌‌888‌,‌888‌‌888‌]

Meeeeeeeeee 8

M8 M8 Meeeeeee ee Meeeeeeeeeeee ee 88 Meeee MeMe Mee
Me M 8 [‌888‌]
MM8MMM8MM8MMM MMM 8 [‌888‌]
MMMM M 8 [‌888‌]

Meeeeeee ee eee ee eeee eeeeeeeee [Me(MM)8(Me8Me)] eeeeeee eeee eeeeeeee eeeeeeeeeeeee [e.e., MMMMe, MMMe, MMe8Me, MeMMM, MM8, MMMM, MeMM8Me, MMMMMe8 ( MMM), MeM] eeeeee eee eeeeeeeeeee eeeee eeeeeeeee.[‌88‌] Mee eeeeeeee eeee eeeeeee ee eeee eeeeee eeeeeeee eee ee eeeeeeeeeee eeeeeee ee eeeeeeeeeee eeeeeeeeeee. Meeee eeeeeee eeeee eeeeeee eeee ee eeeee eeeeeeee Me Me eeeeeeee eee eeeeeeeeeeee eeeeeeee (e.e., ee eeee 88).[‌888‌] Meeeeeeeeeeeeee Me Me Me eeeeee eeeee eeeeeeee eeee eeeeeee eeeeeee (e.e., ee eeee 88)[‌888‌] (eee eeee Meeeeee Meeeeeee Meeeeeeeeee (ee ee 8) eeeee eeee ee eeeeee ee eeeeeee eeeeeeeeeeeeeeee ee eeeeeee 8,8,8,8-eeeeeeeeeeeeeeeeeeeee ee eeee. Me eeeeeeeeeeeee eeeeee (e.e., eeee MMMMe) eeee eeeeeee ee- ee eeeeeeeeeeeeee eeeeeeeee {e.e., [η8-8,8,8-eeee(eeeeeeeeeeeeee)eeeeeee]eeeeeeeeeeeeeeeeeee(8)}.[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeee[η8-8-eeeeee-8-(eeeeeeeeeeeeee)eeeeeee]eeeeeeee(8) (88); Meeeeee Meeeeeeee:[‌88‌]

[Me(MM)8(η8-8-eeeeeeeeeeeee)] (88; 888ee, 8.88eeee) eee eeeeeeeee ee MMM (88eM). Meeee eeeeeee ee 88°M, MeMe (8.8 eeeee) eee eeeee eee eee eeeeeeeee eeeeeee eeeeeee ee eeee eeeeeeeeeee eee 88eee. Me eeeeee ee MMMMe eee eeeee eee eee eeee eeeeeee ee eeee ee ee eeeeeeeee. Mee eeeeeee eee eeeeee eeee 88% ee MM8Me/Me8M, eee eeeeeee eeeeeee eee eeeeeeeee, eeeeee (M8M), eeeee, eee eee eeeeeeee eeee eeeeeeeeee. Meeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/Me8M 88:88), eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeee; eeeee: 888ee (88%); ee 8888°M; MM (MMMe8) νeee: 8888, 8888, 8888, 8888ee8; 8M MMM (MMMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (ee, 8M), 8.88 (ee, 8M).

Meeeeeeeeee[η8-8-(eeeeeeeeeeeeee)eeeeeeeeeee]eeeeeeee(8) (88):[‌88‌]

M eeee ee MMMM eee eeeeeeee ee eeeeeeee ee 8.8M MeMe ee eeeeee (8.88eM, 8eeee) ee e eeee (88°M) eeee ee MMM (8.88eM, 8eeee) ee MMM (8eM). Meeee 88eee, eeee eeee eee eeeeeeeeeee ee e eeeeee-eeeeeeee eeeeeeee eeeeee eeeeeeeeee ee 88°M. Mee MMMM eeee eee eeee eeeee eeeeeeee, eeee e eeeeee ee 88eee, ee e eeee (88°M) eeee ee [Me(MM)8(eeeeeeeeeee)] (88; 888ee, 8eeee) ee MMM (8eM). [Meee: ee ee eeeeeeeee ee eeeeeee eee eeee ee eee eeeeeee ee eeee MMM (e.e., 88°M) eeeeeee ee eee eeeeeeee ee eee eeeeeeeeeee ee 88 ee eee eeeeeeee ee Meeee eeeee.] Meeeee eee eeeeeeee, e eeeee eeeeee eeee eeeeee ee eeee eee eee eeeeeeee. Mee eeee eee eeeeeee e eeeeeee 88eee ee 88°M eee eeee MMMMe (8.888eM, 8eeee) eee eeeee ee eee eeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeee eeeeee eeeeeee ee eee eee eeeeeeeee eeeeeee eeeeeeeee eeee eeeeee. Mee eeee eee eeeeeeee eeeeeee Meeeee eee eee eeeeeeee eeeeeeeeeeee ee eeeee. Meeeeee ee 88°M eeeeeeee eeeeee eeeeeeee ee eee eeeeeee; eeeee: 888ee (88%); ee 888°M; MM (eeeeee) νeee: 8888, 8888, 8888ee8; 8M MMM (eeeeeee-e8, δ): 8.88 (e, 8M), 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M).