You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via1.2.6.1.1.3 Variation 3: C—X Bond Construction (X = Halo)
Please login to access the full content or check if you have access via
Chen, P.; Liu, G.; Engle, K. M.; Yu, J.-Q., Science of Synthesis Knowledge Updates, (2013) 2, 74.
In addition to aromatic C—H arylation and oxygenation, C—H halogenation has also been extensively studied. Fahey reported palladium-catalyzed ortho-halogenation of azobenzene using chlorine and bromine.[76] More recently, Sanford and co-workers reported that a wide range of aromatic compounds with different directing groups can be utilized to give regioselectively halogenated products, e.g. 29, in good yields by using electrophilic N-halosuccinimides as the halogen source and oxidant (Scheme 14).[77,78] Shi and co-workers reported ortho-halogenation of acetanilide derivatives to give products 30 by using a copper(II) halide (CuCl2 or CuBr2) as the halogen source and oxidant (Scheme 14).[79] One mechanistic possibility is that the copper(II) halide coordinates with the cyclopalladated intermediate and transiently oxidizes palladium(II) to trigger reductive elimination.
Meeee, Me eee ee-eeeeeee eeeeeeeee e eeeeeeeeeeeee eeeee-eeeeeeeeee eee -eeeeeeeeeee ee eeeeee eeeee e eeeeeeeeee eeee eeeeeeeee eeeee.[88] Meeeee eeeeeeeeee, eeeeeeeee ee eeee eeee eeeeee eee (eeeeeeeeeeeee)eeeeeee, ee eeee eee eee eeeeeeeeee eeeeeeee ee eeee eeeeeee 88 (Meeeee 88), eeeeeee eeeeeeeeeeeeeeeeee eeeeeee ee eeeeeeeeeeeeeeeeeee eeeeeee eeeeeeeee eee eeee eee eee eeeeeeeeeee eeeeeeee. Mee eeeeeeeeeeeee eeeeeeeeeeeee eeeeeeee eee eeee ee eeeeeeee ee eeee eeeeee eeeee 8 eeeeeeeeeee ee eeeeee eeeeeeeeee. M eeeeeee eeeeeeeeee eeeeeeee eee eeeeeee eeeeeeee ee M-(8-eeeeeeeee)-8,8,8-eeeeeeeeeeeeeeeeeeeeeeeeeee eee 8,8-eeeeeeeeeeeeee (eeeeeeeee) eeeeeeeee eeeeee ee eeee eeeee M—M eeeeeeeeee eeeeeeee eeee ee 88 (Meeeee 88).[88,88]
Meeeee 88 Meeeeeeeeeee ee Meeeee Meeeeeeeee Meeeeeeee Meeeee[88,88–88]
M | Meeee (%) | Mee |
---|---|---|
Me | 88 | [88] |
Me | 88 | [88] |
M | 88 | [88] |
M | Meeee (%) | Mee |
---|---|---|
Me | 88 | [88] |
Me | 88 | [88] |
Meeeeeeee-eeeeeeeee M—M eeeeeeeeeeee eee eeeeeeeee eeeeeeeeeee eeeeeeeee eeeeeeee eee ee eee eeeeeee eeeeeeeeee ee eeeeee eeeeeeeee (Meeeee 88). Meeeeeeeee eeeeeee ee Meeeeee eee ee-eeeeeee eee ee eee eeeee eeeeeeeee-eeeeeeeee M—M eeee-eeeeeee eeeeeeee ee eeee eeeeeeeeeee eeeeeeee eeee ee 88.[88] Me eee eeeeeeee ee eeee 88, e eeeeeeee eeeeeeeeeeee eeeeeeee eeeeeeeee eeeee ee eeee, eeeee ee eeeeeee eee eeeeeeeeeeee eeeeeeeee(MM) eeeeeee (eee eeeee eeeeeeeeeeeeeee) ee eee eeeeeeee ee 8-eeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee (88). Me eee ee-eeeeeee eeee eeeeeee eeeeeeeeeeee eeeeeee, e.e. 8-eeeeee-8,8,8-eeeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee (88), eee e eeeeeeeeeeeeeeeeeeeeeeeeeee eeeeeeeee eeeee ee eeeee eeeeeeeeeee eeeeeeeeeee eeeeeeeeeee 88. Meeeeeee ee 8.8 eeeeeeeeeee ee 8-eeeeeeeeeeeeeeee-8-eee ee eeeeeee eee eeee eeeeeeee.[88] Meee, eeeeeee eeee eeeeeeeeeee eeeeeeeeee e eeeeeeeee M-eeeeeeeee eeeeeeeee eee ee eeeeeeeeeee eeee eeee eeeeee ee eeeeeeeeeeeeeee eeeee e eeeeeee eeeeeeee.[88] Meeee eeeeeeee ee M—M eeee eeeeeeeee eeee eeeeeeee ee eeeeeee eee eeee-eeeeee eeeeeeeeeeeee. Meeeeeee eee eee eeeeeeeee ee eeee eeee(eeeeee)eeeeeeeee(MM) [Me(MM)(Me8)(M)] eeeeeeeee eee eeee eeeeee eeeeeee eeeeeeeeeee eeeeeee ee eeeeeeee eeeeeeeee.[88,88]
Meeeee 88 Meeeeeeeeeee ee Meeeee Meeeeeeeee Meeeeeeee Meeeee[88,88]
Meeeeeeeeeee Meeeeeeee
8-(8-Meeeeeeeeeee)-8-eeeeeeeeeeeeee (88, M = Me); Meeeeee Meeeeeeee:[88]
8-Meeeee-8-eeeeeeeeeeeeee (888 ee, 8.888 eeee), MMM (88.8 ee, 8.888 eeee), eee Me(MMe)8 (8.8 ee, 8.888 eeee) eeee eeeeeeee ee e 88-eM eeee. MeMM (8.8 eM) eee eeeee, eee eeee eee eeeeee eeee e Meeeee-eeeee eee, eee eee eeeeeee eee eeeeee ee 888 °M eee 88 e. Mee eeeeeee eee eeeeee ee ee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeeee ee MM8Me8, eeeeeeee eeeeeee e eee ee eeeeee eee, eee eeeeee eeee eeeeeee/MeMMe (8:8; 888 eM). Mee eeeeeeee eee eeeeeeeeeeee eee eee eeeeeeeee eee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/MM8Me8). Mee eeeeeee eee eeeeeeee ee e eeeee eee; eeeee: 88 ee (88%); Me 8.8 (MeMMe/MM8Me8 8:88).
8,8,8-Meeeeeeee-M-[8-(8-eeee-8-eeeeeeeeeeee)eeeee]eeeeeeeeeeeeeeeeee (88); Meeeeee Meeeeeeee:[88]
Me e 88-eM eeeeee eeee, 8,8,8-eeeeeeeee-M-[8-(8-eeeeeeeeeeee)eeeee]eeeeeeeeeeeeeeeeee (88; 88.8 ee, 8.8 eeee), Me(MMe)8 (8.8 ee, 8.88 eeee), MeM(MMe)8 (888.8 ee, 8.8 eeee), M8 (888.8 ee, 8.8 eeee), eee MeMMM8 (88.8 ee, 8.8 eeee) eeee eeeeeeeee ee eeeee MMM (8 eM) eeeee eee. Mee eeee eee eeeeee eeee e Meeeee-eeeee eee, eee eee eeeeeee eee eeeeeee ee 888 °M eee 88 e. Mee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe) eeee eee eeeeeee ee e eeeee eeeee; eeeee: 88.8 ee (88%).
8,8,8-Meeeeeeee-M-(8-eeeeee-8-eeeeeeeeeeee)eeeeeeeeeeeeeeeeee (88, M8 = Me); Meeeeee Meeeeeeee:[88]
Me e 88-eM eeeeee eeee, 8,8,8-eeeeeeeee-M-(8-eeeeeeeeeeee)eeeeeeeeeeeeeeeeee (88.8 ee, 8.8 eeee), Me(MMe)8•8M8M (8.8 ee, 8.88 eeee), 8-eeeeee-8,8,8-eeeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee (88; 88.8 ee, 8.8 eeee), eee MMM (88 μM, 8.8 eeee) eeee eeeeeeeee ee eeeee 8,8-eeeeeeeeeeeeee (8.8 eM) eeeee eee. Mee eeee eee eeeeee eeee e Meeeee-eeeee eee, eee eee eeeeeee eee eeeeeee ee 888 °M eee 8.8 e. Meeee eee eeeeeee eee eeee eeeeee ee ee, ee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe); eeeee: 88.8 ee (88%).
References
[20] | Meee, M. M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[21] | Meeeee, M.; Meeeee, M., M. Me. Meee. Mee., (8888) 888, 88 888. |
[76] | Meeee, M. M., M. Meeeeeeee. Meee., (8888) 88, 888. |
[77] | Meeeeee, M.; Meee, M. M.; Meeee, M. M.; Meeeeee, M. M., Mee. Meee., (8888) 8, 8888. |
[78] | Meeeeee, M.; Meee, M. M.; Meeee, M. M.; Meeeeee, M. M., Meeeeeeeeee, (8888) 88, 88 888. |
[79] | Mee, M.; Me, M.; Me, M.; Meeee, M.; Mee, M.; Meeee, M.; Mee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[80] | Mee, M.-M.; Meee, M.; Meeeee, M.; Me, M.-M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[81] | Me, M.-M.; Mee, M.-M.; Me, M.-M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[82] | Me, M.-M.; Meee, M.; Me, M.-M., Meeeeeeeeee, (8888) 88, 8888. |
[83] | Meee, M. M.; Meeee, M. M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[84] | Meee, M.; Mee, M.-M.; Me, M.-M.; M. Me. Meee. Mee., (8888) 888, 8888. |
[85] | Meee, M. M. M.; Meee, M.; Meee, M.; Me, M.-M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |