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Please login to access the full content or check if you have access via2.6.1.7 Palladium-Catalyzed Ligand-Directed C—H Fluorination of Benzamide Derivatives
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McMurtrey, K. B.; Sanford, M. S., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013) 2, 560.
A related procedure has recently been developed for the tetrakis(acetonitrile)palladium(II) trifluoromethanesulfonate catalyzed ligand-directed C—H fluorination of benzamides with 1-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate (NFTPT) (Scheme 7).[9] Variation of the amide nitrogen substituent enables the tuning of selectivity for mono- versus difluorination. Use of the 2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl-substituted amides 13 results in >10:1 selectivity for monofluorination. Isolated yields of monofluorinated products 14 in this transformation range from 36 to 78%. The scope and functional group tolerance are similar to those of the related transformations in Sections 2.6.1.5 and 2.6.1.6.
Meeeee 8 Meeeeeee Meeeeeeeeeee ee Meeeeeeee M—M eeeee ee e Meeeeeeee-Meeeeeeee Meeeeee[8]
M8 | M8 | M8 | Meee (e) | Meeee (%) | Mee |
---|---|---|---|---|---|
M | M | M | 8 | 88 | [8] |
M | M | e-Me | 8 | 88 | [8] |
Me | M | M | 8 | 88 | [8] |
M | Me | M | 8 | 88e | [8] |
M | M | MMe | 88 | 88e | [8] |
M | M | MMe | 8 | 88 | [8] |
M | MMe | M | 88 | 88 | [8] |
M | M | M | 8 | 88e | [8] |
Me | M | M | 88 | 88 | [8] |
M | Me | M | 88 | 88 | [8] |
M | M | Me | 88 | 88 | [8] |
M | Me | M | 88 | 88 | [8] |
M | M | Me | 88 | 88 | [8] |
MM8 | M | M | 8 | 88e | [8] |
M | M | MM | 88 | 88 | [8] |
M | M | Me | 88 | 88 | [8] |
e Mee eeeeeeee eee eee ee 888 °M.
e MeMM8 (8 eM) eee eeee ee eeeeeee, eeee MMM (88 eee%).
Meeeeeeeeeee Meeeeeeee
8-Meeeee-M-[8,8,8,8-eeeeeeeeeee-8-(eeeeeeeeeeeeeee)eeeeee]eeeeeeeee (88, M8 = M8 = M8 = M); Meeeeee Meeeeeeee:[8]
Me e 88-eM Meeeeee eeee, M-[8,8,8,8-eeeeeeeeeee-8-(eeeeeeeeeeeeeee)eeeeee]eeeeeeeee (88, M8 = M8 = M8 = M; 88.8 ee, 8.8 eeee), Me(MMMe)8(MMe)8 (8.8 ee, 8.88 eeee), MMMMM (88.8 ee, 8.88 eeee), eee MMM (8.8 ee, 8.88 eeee) eeee eeeeeeeee ee eee MeMM (8.8 eM) eeeee M8. Mee eeee eee eeeeee eeee e Meeeee-eeeee eee, eee eee eeeeeee eee eeeeee ee 888 °M eee 8 e. Meeee eeeeeee ee ee, eee eeeeeeeee eeee eee eeeeeeeeeeee eeeee eeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe eeeeeeee). Meeeeee eeeeeeeeeeee eee eeeeeee eee ee eeeeeeeeeee MMM (eeeeeee/MM8Me8 8:8), eeeeeeeee eee eeeeeee ee e eeeee eeeee; eeeee: 88.8 ee (88%).
References
[9] | Meee, M. M. M.; Meee, M.; Meee, M.; Me, M.-M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |