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Please login to access the full content or check if you have access via1.4.2.3.1.1.2 Magnesiation and Zinc Transmetalation before Cross Coupling
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Undheim, K., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013) 1, 733.
The synthesis of cross-coupled products by magnesium insertion into hetaryl bromides in the presence of lithium chloride and zinc(II) chloride is initiated by a lithium chloride promoted insertion of magnesium followed by treatment with electrophiles.[29] Lithium chloride serves several purposes: (i) it solubilizes the resulting organozinc compound and thus provides a clean metal surface; (ii) it promotes the initial electron transfer by electrophilic activation of the aromatic ring through complex formation; and (iii) the high ionic strength of lithium chloride solutions facilitates charge separation and accelerates the metal insertion.
Me eee eeee ee 8-eeeee-8-eeeeeeeeeeeeee (88), eeeeeeeee eeee eee M—Me eeee ee eeeee eeeeeeeeeeeeee (Meeeee 88).[88] Meeee eeeeeeeeeeee eee eeeeeeeeee eeeeeeeee, eeeeeee 88 ee eeeeeeee eeeee 88 eeeeeee ee 8 °M. Meeeeeeee-eeeeeeeee eeeee eeeeeeee eeee 8-eeeeeeeeeee eeeee eee eeeeee eeeeeee 88 ee 88% eeeee.
Meeeee 88 Meeee Meeeeeee ee Meeeeeeeeee Meeeeee eeeee M—M Meeeeeeeeeee eee Meeeeeeeeeeeee[88]
Meeeeee-eeeeeeeeeee π-eeeeeeeee eeeeeeeee eeeeeee eeeeeee eeeeeeeeeeee eeeeeeeeeeee eeeeeeeee. Meeeeeeeeee, eeee- eee eeeeee-8,8,8-eeeeeeeee eeeeeee eeeeeee eeeeee–eeeeeeeee eeeeeeee eeee eeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeee eeeeeee ee eee eeeeeeeeeeee eeeeeeeeee eeeeeeeeeeeeeeee eeeeeeeeeee eeee eee eeeeeeeeeeee eeeeeeeeeeeeee eeee eeee(MM) eeeeeeee.[88] Meeeeeee ee eee eeeee eeeeeeeee eeeeee eeeeeee, eeeeeeeeeeeeeeeeee eeeeeeee, Meeeeeee eeeeeeee eeee ee eeeeeeeeeeeeee eeeeeeee eee eeeeeeeeeeeeee eeeeeee eee eeee eeeeeeeeeeee eee eeee eeeeeeeee, eeee eeeeeeee eeeeeeee eeeeeeeeeeee eeeeeeee. Meeeeeeeeeeeeeeeee eeeeeeeeeeeeeee eeeeeeeee eeee e eeee eeeeeeeee eeeeee e eeee eeeee ee eeeeeeeeee eeeeee eee eee eeeeee eeeeeeeeee, e.e. eee eeeeeee–eeeeeeeee ee eeeeee–eeeeeeeee eeeeeeee eeeeeeeee, ee eeeee eeeee. Mee eeeeeeeeeeeee eeeeeeee 8,8,8-eeeeeeeee eee eeeeeeeee eeee eee eeeeeeeeeee eeeeeeeeee eeeee eeeeeeeeeeeeeee eeee eeee(MM) eeeeeeee.
Me eee eeeee eeeeeee eeeeeeeee ee Meeeee 88, 8-eeee-8,8-eeeeeeee-8,8,8-eeeeeeee eeeeeeeee e eeeeee eeeeee–eeeeeeeee eeeeeeee eeee eeeeeeeeeeeeee eeeeeeee (8.8 eeeee, −88 °M, 88 eee). Meeee eeeeeeeeeeeeeee eeee eeee(MM) eeeeeeee (8.88 eeeee, 88 eee) eee eeeeeeeeeeeee 8,8,8-eeeeeeeeeeeee eeeeeeee 88 ee eeeeeeee (>88% eeeee). Meeeeeeeee eeeeeeeee(8)-eeeeeeeee eeeee eeeeeeee eeee eee eeee eeeeeeeeeeee (8.8 eeeee, −88 °M ee 88 °M, 88 e) eeeeeeee eee eeeeeee eeeeeeee 88 ee 88% eeeee. Meeeeeeee, ee eeeeee–eeeeeeeee eeeeeeee eeeeeeee ee eeeee 8-(8-eeee-8-eeeeee-8,8,8-eeeeeee-8-ee)eeeeeeee (88) eeee eeeeeeeeeeeeee eeeeeee eeeeee eee eeeeeeeeeee eeeeeeeeeeee, eeeee, eeeee eeeeeeeeeeeeeee eeee eeee(MM) eeeeeeee, eeeeeeee eee eeeeeeeeeeeee eeeeeee. M eeeeeeeeee Meeeeee eeeeeeee eeeee 8 eee% ee eeeeeeeee eeeeeee 88 (MMMMMM-MMe) ee eeee eeeeeeeeeee eeeeeee eee eeeeeeeeeeeee eeeeeeeeeeeeee 8,8,8-eeeeeeee 88 ee 88% eeeee (Meeeee 88).
Meeeee 88 Meeee Meeeeeee ee Meeeeeeeeee Meeeeee eeee Meeeeeeee eeeee M—M Meeeeeeeeeee eee Meeeeeeeeeeeee[88]
Mee Meeeeee eeeee-eeeeeeee eeeeeeee eeee eeeeeeeeeee eeeeeeeee ee eeeeeeeee eeeeeeeee ee eeeeeee. Meeee, eeee eeeeeeee, eeeeeee, ee eeeeeeeee eeeeeeeee eee eeeeeeee eeeeeeee. Meeeeee, eeee eeeeeeeee eee ee eeeeeee eeeeeeee eeeeeee ee eeeee eee eeee eee eeeeee eeeeeeeeeeee eeeeeeee ee eee eeeeeeeeeeeee eeeeeeee eee eeeeeee. M eeee eeeeee eeeee ee Meeeeeee-eeee eeeeeee ee Meeeeee eeeee eeeeeeeee eeeeeee 8-eeeeeeeeeee eeeeeee eee eeee eeeeeeeee eee eeeee eeee eee eeeeeeee-eeee Meeeeeee-eeee eeeeeee eeee eeee eeeeeeeeee.[88] 8-(Meeeeeeeeeeeeeeeeeeee)-8′,8′,8′-eeeeeeeeeeeeeeeeeeee (MMeee) eeeeeeee eee eeee eeeeeeeee eeeeeeee eeeeee eee eeeeeeee eeeeeeeeee ee eeee eeeeeeeeeeeeee. Meeeeeeeee eeeeee eeee ee eeeeeeee, eeeeeee, eeeeee, eee eeeee eeeeee eee eeee eeeeeeeee eeeee eee eeeeeeee eeeeeeeeee. Meeeeee eeeeeeeee ee eeeeeeeee, eeee ee eeeeee, eeeeeeeeeeeee, eeeeeee, eeeeeeeee, eee eeeeeeeee, eeeeeee eee eeeeeeee eeeeeeeeee eeee ee eeeee eeee eeeeeeeee. Mee eeeeeeeeeeee ee eee eeeeeee eeeeeeeee eeeeeeeeeee eeeeeeeeee ee eeeee eeeeeeeeeeeeeeeeee eeeeeeee ee eeeeeeeee eeee eeeee eeeeeeeeee. Mee eeeeeeeeee eeeeeee ee eeeeeeeeeee eee ee eeee eeeeeeeeeeeeeee ee eeeeeeee eee Meeeeeee eeeeeeee eeee e eeeeeeee ee eeee(MM) eeeeeeee ee eeeeeee eeeeeeeeeee. Mee eeeeeee eeeeeeee eee eeeeeeeeeeee eeeeeeee eee eee Meeeeee eeeee-eeeeeeee eeeeeeeee eeee eeeeeee eeeeeeeee. Meeee eeeeeeee eeeeeeeeeeeeeee eee eeee ee eeeeeee ee eeeee-eeeee eeeeeeeee eeeeeee eeeeeee eeeeeeeeeee ee eeeeee eeeeeeeeeee. Me eeeeeeeee ee Meeeee 88, 8-eeeeeeeeeeeeee ee eeeeeeee eee eeeee eeeeeee eeee 8-eeeeeeeeeeeeee ee eeee eee eeeeeee 88 ee eeeeeeeee eeeee. Meeeeeeee, 8-eeeeeeeeeeeee eee 8-eeeeeeeeeeeeeee eeeeee eee eeeee-eeeeeee eeeeeee 88 ee eeee eeeee.[88]
Meeeee 88 Meeee Meeeeeee ee Meeeeee Meeeeeeee eeee Meeeeeeeeee Meeeeee[88]
Meeeeeeeeeee Meeeeeeee
8-Meeeee-8-(8-eeeeeeeeeeeee)eeeeeeee (88); Meeeeee Meeeeeeee:[88]
Me eeeeeeee (888 ee, 8 eeee) eeee eeeeee ee e eee Meeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee e eeeeee eeeee eeeeee. 8.8 M MeMe ee MMM (8.8 eM, 8.8 eeee) eee eeeee, eee eee Me eee eeeeeeeee eeee e 8.8 M eeee ee MMMMM-M ee MMM (8.8 eM, 8.88 eeee). Mee eeeeeeeee eeeeeee eee eeeeeee eee 8 eee, eeeeee ee 8 °M, eee 8-eeeee-8-eeeeeeeeeeeeee (88; 888 ee, 8 eeee) eee eeeee ee eee eeeeeee. Mee eeeeeee eee eeeeeee eee 88 eee eee eeee eeeeeeeeeee eeee e eeeeeee ee e 8 M eeee ee MeMe8 ee MMM (8 eM, 8.8 eeee) ee 8 °M. Meee eeeeeee eee eeeeeee ee 8 °M eee 88 eee eeeeee Me(eee)8 (88 ee, 8 eee%), (8-eeeee)8M (88 ee, 8 eee%), eee 8-eeeeeeeeeee (888 ee, 8,8 eeee) eeee eeeee. Mee eeeeeee eee eeeeee ee 88 °M eee eeeeeee ee eeee eeeeeeeeeee eee 8 e. Mee eeeeeeee eee eeee eeeeeeee eeee eee. ee MM8Me (88 eM) eee eee eeeeeee eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8) eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeee eeeeee eeeeeeeeeeeeee ee eee eeeeeee (eeeeee eee, MM8Me8) eeee eee eeeeeee ee e eeeeeeeee eeeee; eeeee: 888 ee (88%).
8,8′,8,8′-Meeeeeeeeee-8,8′-ee-8,8,8-eeeeeeee (88); Meeeeee Meeeeeeee:[88]
M eee, eeeee-eeeeeee Meeeeee eeeee, eeeeeeee eeee e eeeeeeee eeeeeee eee eee e eeeeee, eee eeeeeee eeee 8-eeee-8,8-eeeeeeee-8,8,8-eeeeeeee (888 ee, 8 eeee) eeeeeeee ee eeeeeeee eeeeeeee ee e 8.88 M eeee ee MeMeMe ee MMM (8.88 eM, 8.8 eeee) ee −88 °M. Mee eeeeeee eee eeeeeee eee 88 eee ee eee eeee eeeeeeeeeee. Meeeeeee eeeeee–eeeeeeeee eeeeeeee eee eeeeeeeee ee MM eeeeeeee ee eeeeeeee eeeeeeee eeeeeeee eeee eeeee, eeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee. Meeee eeeeeeee ee 8 M MeMe8 ee MMM (8.8 eM, 8.8 eeee) ee −88 °M eee eeeeeeee eee 88 eee, e eeee ee 8-eeee-8,8-eeeeeeee-8,8,8-eeeeeeee (888 ee, 8 eeee) eee Me(MMe8)8 (88 ee, 8 eee%) ee MMM (8 eM) eee eeeee. Mee eeeeeee eee eeeeee eeeeee ee 88 °M eeee eeeeeeeeee eeeeeeee eee 88 e. Mee eeeeeeee eee eeeeeeee eeee eeeee (8 eM), eee eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 88:8) eeeeeeee eee eeeeeee ee e eeeeee eeeee; eeeee: 888 ee (88%); ee 888.8–888.8 °M.
Meeeeee 8,8′-{8,8′,8′′-Meeeeeeee-[8,8′:8′,8′′-(eee-8,8,8-eeeeeeee)]-8,8′′-eeee}eeeeeeeeee (88); Meeeeee Meeeeeeee:[88]
M 8-M, eeeee-eeeeee, eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee, e eeeeee eeeeeeeee, ee eeeeeeee eeeeee, eee e eeeeeeeeeee eee eeeeeee eeee Me eeeeeeee (88.8 e, 8.888 eee). Mee eeeee eee eeeeee eeeeee (88 °M) eeeee eeeee eeeee eee Me eeeeeeee eeee eeeeeeeeee eeeeeee eee 8 e ee eeeeeeee eee Me eeeeeee. Mee eeeeeee eee eeeeee ee 88 °M eee MMM (88 eM) eee eeeee eeeee eeee ee. 88 eM ee e eeee ee 8-eeeeeeeeeee (88.8 e, 8.88 eee) ee MMM (888 eM). Mee eeeeeeee eeeeeee eeeee ee. 8–8 eee ee eee eeeeeee eeeeeeeeee, ee eeeeeeeee ee e eeeee eeee ee eee eeeeeeeeeee. Meeeeeeeee, eee eeeeeeeee eeee ee 8-eeeeeeeeeee eee eeeee eeeeeeee eeee e eeeeee ee 8 e eeeee eee eeeeeeeeeee eee eeee eeeee 88 °M. Mee eeeeeee eee eeeeeee eee ee eeeeeeeeee 8 e eeeeee eee eeeeeeeeeee eeee eee eeeeeeeeee eeee e eee, eeeee-eeeeeee Meeeeee eeeee. Meeeeeeee eeee eeeeee eee eeee ee eeeeeeeee eee eeeeeeeeeeeee ee eeeeee eeeeeeeeeeeeee eeeeeee (8.8 M).
M eee, eeeee-eeeeeee Meeeeee eeeee, eeeeeeee eeee e eeeeeeee eeeeeee eee eee e eeeeee, eee eeeeeee eeee eeeee 8-(8-eeee-8-eeeeee-8,8,8-eeeeeee-8-ee)eeeeeeee (88; 888 ee, 8 eeee) ee MMM (8 eM) eeeeeeee ee eeeeeeee eeeeeeee ee e eeee ee eeeeeeeeeeeeee eeeeeee ee MMM (8.8 eeeee) ee −88 °M. Mee eeeeeee eee eeeeeee eee 88 eee eeeeee e eeee ee 8,8-eeeeee-8-eeeeee-8,8,8-eeeeeeee (888 ee, 8.88 eeee) eee eeeeeeeee eeeeeeee 88 (88 ee, 8 eee%) ee MMM (8 eM) eee eeeee, eeeeeeee ee eeee eeeeeee ee 88 °M eee eeeeeeeeee eeeeeeee eee 88 e. Mee eeeeeeee eee eeeeeeee eeee eeeee (8 eM) eee eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 8:8) eeeeeeee eee eeeeeee ee e eeeeee eeeee; eeeee: 888 ee (88%); ee 888.8–888.8 °M.
8-(8-Meeeeee)eeeeeeee (88); Meeeeee Meeeeeeee:[88]
M eeeee-eeeeee, eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeee eee eee eeeeeee eeee e 8.8 M eeee ee eMeMeMe ee MMM (8.88 eM, 8.8 eeee, 8.8 eeeee). Me eeee eeeeeee eee eeeee eeee 8-eeeeeeeeeeeeee (8.888 eM, 8.8 eeee, 8.8 eeeee) eeeeeeee eeee eee eeeeeeeeeee eee eeeeeeeee 88 °M. Meeee 8–8 e, e 8.8 M eeee ee MeMe8 ee MMM (88 eM, 8.8 eeee, 8.8 eeeee) eee eeeee eeeeeeee eeee eee eeeeeeeeeee eee eeeeeeeee 88 °M. Meeee 8 e ee ee, eee eeeeeee eee eeee ee eeee eee eeeeeeeeee eeeee eeeeeeee.
M eeee ee Me8(eee)8 (88.8 ee, 8.88 eeee, 8 eee%) eee MMeee (88.8 ee, 8.88 eeee, 8 eee%) ee MMM (8.8 eM) eeeee M8 eee eeeeeee eee eeeeee ee 88 °M eee 88 eee. Me eeee eeee eee eeeee 8-eeeeeeeeeeeeee (8 eeee). Meeee eee eeeeeee eee eeee eeeeeee eee 88 eee, eee eeeee eeeeeeee eeeeeeeeee eeeeeee (8.8 eeee) eee eeeee eeeeeeee. Mee eeeeeeee eee eeeeeeeee ee MMMM eee/ee MMM, eee, eeee eeeeeeeeee, eee eeeeeee eee eeeeee ee ee. Mee eeeeeeee eee eeee eeeeeeee eeee eee. ee MeMMM8 (8 eM) eee M8M (8 eM). Meeee eeeeeeeeee, eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8 ×). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M, eeeee (MeMM8), eee eeeeeeee, eee eee eeeeeee eee eeeeeee ee eeeeee eeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee eeeeeeee); eeeee: 88%.
8-(8-Meeeeee)eeeeeeee (88); Meeeeee Meeeeeeee:[88]
M eeeee-eeeeee, eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeee eee eee eeeeeee eeee 8.8 M eMeMeMe ee MMM (8.88 eM, 8.8 eeee, 8.8 eeeee). Me eeee eeeeeee eee eeeee eeee 8-eeeeeeeeeeeee (8.888 eM, 8.8 eeee, 8.8 eeeee) eeeeeeee eeee eee eeeeeeeeeee eee eeeeeeeee 88 °M. Meeee 8–8 e, 8.8 M MeMe8 (88 eM, 8.8 eeee, 8.8 eeeee) eee eeeee eeeeeeee eeee eee eeeeeeeeeee eee eeeeeeeee 88 °M. Meeee 8 e ee ee, eee eeeeeee eee eeee ee eeee eee eeeeeeeeee eeeee eeeeeeee.
M eeee ee Me8(eee)8 (88.8 ee, 8.88 eeee, 8 eee%) eee MMeee (88.8 ee, 8.88 eeee, 8 eee%) ee MMM (8.8 eM) eeeee M8 eee eeeeeee eee eeeeee ee 88 °M eee 88 eee. Me eeee eeee eee eeeee 8-eeeeeeeeeeeeeee (8 eeee). Meeee eee eeeeeee eee eeee eeeeeee eee 88 eee, eee eeeee eeeeeeee eeeeeeeeee eeeeeee (8.8 eeee) eee eeeee eeeeeeee. Mee eeeeeeee eee eeeeeeeee ee MMMM eee/ee MMM, eee, eeee eeeeeeeeee, eee eeeeeee eee eeeeee ee ee. Mee eeeeeeee eee eeee eeeeeeee eeee eee. ee MeMMM8 (8 eM) eee M8M (8 eM). Meeee eeeeeeeeee, eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8 ×). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M, eeeee (MeMM8), eee eeeeeeee, eee eee eeeeeee eee eeeeeee ee eeeeee eeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee eeeeeeee); eeeee: 88%.
References
[29] | Meeeee, M. M.; Meeeeeeeeee, M.; Meeeeeeeee, M.; Meee, M.; Meeeeee, M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[30] | Meee, M.; Meee, M. M.; Meeeeee, M., Mee. Meee., (8888) 88, 8888. |
[31] | Meeeee, M. M.; Meeee, M. M.; Mee, M., M. Mee. Meee., (8888) 88, 8888. |