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Please login to access the full content or check if you have access via26.8.4.1.1.1.5 Variation 5: With Brønsted Acid Catalysts
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Sellars, J. D., Science of Synthesis Knowledge Updates, (2014) 1, 406.
Whilst arenes and acid chlorides or anhydrides are typically reacted with metal catalysts to form aryl ketones, both homogeneous and heterogeneous Brønsted acids represent viable alternatives. Homogeneous acids such as trifluoromethanesulfonic acid, generated in situ from the reaction of a carboxylic acid and trifluoromethanesulfonic anhydride, catalyze the coupling of electron-rich arenes with the newly formed mixed anhydride to yield aryl ketones (e.g., 6) in good yield (Scheme 14).[43] Other anhydrides have been utilized, such as methanesulfonic anhydride (e.g., in the synthesis of sulfonyl ketone 7; Scheme 14)[44] and trifluoroacetic anhydride (e.g., in the formation of β-oxo phosphonate 8; Scheme 14).[45] N,N′-Bis(trifluoromethylsulfonyl)trifluoromethanesulfonodiimidic acid (9) is another homogeneous Brønsted acid which has found utility as a catalyst (1 mol%) in the synthesis of aryl ketones due to its extreme acidity (Scheme 14).[43–49]
Meeeee 88 Meeeeeeeeee Meøeeeee Meee Meeeeeeee Meeeeee–Meeeee Meeeeeeee[88–88]
Meeeeeeeeeeee Meøeeeee eeeee eeee eeee eeee eeeeeeee. Meeeeeeeeeeee eeeeeeeeeeeee eeeee eee eeeeee eeeeeeee eeee eee eeee ee eeeeeee eeeeeeee-eeee eeeeee eeee eeeeeeeeee ee eeeeeee eeee eeeeeee ee eeee eeeee.[88,88] Meeeeeeee, eeeeeeee, eeeeeeeeeee eeeeee eeeeeeee ee eeeeeeeeeeeeeeee, eee eeeeeeee eeeeeeee ee eeeeeeeeee ee eeeeeeee, eeee eeeeeee ee eeeeeeeee eeeeeeeeeeeee eeeeeeeee eee eeee eeeeeeeeeeeeee.[88–88] Meeee eeeeeeeeeeeeeee eeee eeeeeee Meøeeeee eeeee ee Meeee eeeee ee ee eeeeeeee ee eee eeeeeee eeeeee eeee eeeeeeeee eeeeeeeee eee Meeeeee–Meeeee eeeeeeeee. Mee eeeeeee, MMM-8 eee M-eeee eeeeeeee eeeeeee eeeeeeeeeee eeeeeee eee eeee eeeeeeeeeeee eeee eeeeeeee eeeeeee ee eee eeeeeeee ee eeeeeeee-eeee eeeeee eeee eeee eeeeeeeee.[88] MMM-8 eee eeee eeeeeeeeeeee eeee eeeeeeeee eeeeeeee eeee eeeeeeee-eeee eeeeee eee eeeeeeeeee (Meeeee 88).[88] Me eeeeeeee, MM eeeeeeee eeeeeeeeee eeeeeeeeeeee eeeee eeeeee ee eeeeee eee/eeeeeee (8, 88, eee 888 eeeeeeeeeeee) eeee eeeee eeeeeee, eeeeee eeee eeeeeee eeeeee eeeeeeeeee eee eeee eee e eeeeeeee eeeeeee eeeeeee Meøeeeee eee Meeee eeeeee eeeee.[88] Meeee eeeeeee eeeeeeeee eeeeeee MMM-88, eeeee ee eeee ee eeeeeee eeeeeeee-eeee eeeeee eeee eee eeee eeeeeee ee eeee eeeee eee eeee eeee eeeeeeeeeeeeeeee ee eeeeeeee eeee eeeeeeeeee (Meeeee 88).[88]
Meeeee 88 Meeeeeeee Meeee Meeeeeee eee Meee Meeeeeeeee[88,88]
Meeeeeeeee | Meeee (eeeee/eeee/eeee) | Meeee (%) | Mee |
---|---|---|---|
MMM-88, eeeeeeeeeeee, 888 °M | 8:8:88 | 88 | [88] |
MMM-8, eeee, 88 °M | 8:8:88 | 88 | [88] |
Meeeeeeeeeee Meeeeeeee
8-(8-Meeeeeeeeeeee)eeeeeeee (8); Meeeeee Meeeeeeee:[88]
Me8M (8.88 eM, 8 eeee) eee MeMM (8 eeee) eeee eeeee eee eeeeeee ee ee. Mee eeeeeee eee eeeeee eeeee eee eeeeeeeeeee eee eeeeee ee 88 °M, eee eeee MeMM (8 eeee) eee eeeee eee eee eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee MMM. Me eeeeeeeeee ee eee eeeeeeee, eee eeeeeee eee eeeeee eeee ee MeMMM8 (88 eM) eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8). Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeee eeeeee ee eeeeee eee, eeeeee/MeMMe 8:8); eeeee: 88%.
8-(8-Meeeeeeeeeee)-8-[8-(eeeeeeeeeeeeeee)eeeeee]eeeeeeee (8); Meeeeee Meeeeeeee:[88]
Me (8-eeeeeeeeeee)eeeeee eeee (8 e, 88.8 eeee, 8 eeeee) eee eeeee eeeeeeeeeeeee (8.8 eM, 88.8 eeee, 8.8 eeeee), eeeeeee (88 eM), eee Me8M (8.88 e, 88.8 eeee, 8.8 eeeee). Mee eeeeeee eee eeeeee ee 88 °M eee 8 e. Meeeeeeeee eeeeeeeeee eeeeee (8 eM) eee eeeee eeeeeeee, eee eee eeeeee eee eeeeee ee eeeeee eee 8 eee, eeeeee ee 88 °M eeee 88 eee, eeeeeee ee 8 °M eee 88 eee, eee eeee eeeeeeee ee eeeeeeeeee. Mee eeee eee eeeeee eeee eeeeeee eeeeeee eeeeeeeeee eeeeeeeeee eeeeee (8 eM, eeee 8 eM), eeeee eeeeeeeeee, eeeeee eeee M8M (88 eM), eeeee eeeeeeeeee, eee eeee eeeee ee eeeeeeee eeeeee ee e eeeeee eeee; eeeee: 8.88 e (88%).
Meeeeeee [8-(8,8-Meeeeeeeeeeeeee)-8-eeeeeeee]eeeeeeeeeee (8); Meeeeee Meeeeeeee:[88]
M 88-eM eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeeeee eeee 8,8-eeeeeeeeeeeeeeee (8.88 e, 88 eeee) eee MMMM (8.8 eM, 88 eeee). Mee eeeeeee eee eeeeee ee 8 °M eeee eeeeeeee eee eeeeeee eeee (eeeeeeeeeeeeeeeeeee)eeeeee eeee (8.88 e, 88.8 eeee) eeeeeeee ee 88% M8MM8 (8.88 e, 88.8 eeee). Meeee 8 eee, eee eee eeee eee eeeeeee, eee eee eeeeee eeeeeee eee eeeeeee ee ee. Meeee 88 e, eee eeeeeee eee eeeeee ee 8 °M eee eeeeeee eeee M8M (88 eM). Meee, eee eM eee eeeeeeee ee ee. 8 ee eee eeeeeee eeeeeeee ee 88 M ee MeMM (ee. 88 eM). Mee eee eeee eee eeeeeee, eee eee eeeeeee eee eeeeeee eee 88–88 eee eeeeee ee eee eeeeeeeee eeee eeeeeee (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeee eeeeeeeee eeee 8 M ee MeMM (8 × 88 eM, eeee 8 × 88 eM). Mee eeeeeeee MeMM eeeeeeee eeee eeeeeeeee ee eM <8 ee eee eeeeeeee ee eeeee MMe (ee. 8 eM). Meee eeeeeeeee eeeeeee eeeee eee eeee eeeeeeeee eeee MM8Me8 (8 × 88 eM, eeee 8 × 88 eM). Mee eeeeeeee MM8Me8 eeeeeeee eeee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeeeee ee e eeee eeeeee eee; eeeee: 8.88 e (88%).
References
[43] | Meeeeee, M. M.; Meeeee, M., Meee. Meeeee Meee. Mee., (8888) 88, 8888. |
[44] | Meeeeeeee, M. M., Mee. Meee., (8888) 88, 8888. |
[45] | Meee, M. M.; Meeeeee, M. M.; Meee, M.-M.; Meeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[46] | Meeeeee, M. M.; Meeeeeee, M.; Meeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[47] | Meeeeeeeeee, M.; Meeeeeee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[48] | Meeeeee, M. M.; Mee, M. M., Mee. Meee., (8888) 88, 8888. |
[49] | Meeeeeeee, M. M.; Meeeeeeeeeeee, M. Me.; Meeeeeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 888. |
[50] | Meeeee, M., Meeee. Meeeee., (8888) 8, 888. |
[51] | Meeeeeee, M.; Meeeeee, M. M.; Meeeee, M., Meee. Meeeee Meee. Mee., (8888) 88, 8888. |
[52] | Meeeeeeeeee, M. M., Meee. Meeee., M, (8888) 888, 888. |
[53] | Meeeeáeeeeá, M.; Meeeeřeeeá, M.; Meeeeeeeá, M., Meeee. Meeee, (8888) 888, 88. |
[54] | Meeee, M. M.; Meeee, M.; Meeeeee, M. M., MM 8888 888 888, (8888); Meee. Meeee., (8888) 888, 888 888. |
[55] | Meeeee, M. M.; Meeee, M. M., Meeee. Meee., (8888) 88, 888. |
[56] | Meeeeeeeeee, M.; Meeeee, M.; Mee, M. M.; Meee, M. M., Meee. Mee. Meeeeee., (8888) 88, 888. |
[57] | Meee, M.; Meeeeee, M.; Meeee, M.; Meeee, M.; Meeeeeeee, M.; Meeeeeee, M.; Meeeeee, M., M. Mee. Meeee. M: Meee., (8888) 888, 888. |
[58] | Meeeeeee, M.; Meeee, M.; Meeeeee, M., Meeee. Meee., (8888) 888, 88. |