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Please login to access the full content or check if you have access via20.2.1.7.5 Method 5: The Benzil–Benzilic Acid Rearrangement
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Phillips, A. J.; Love, C. E., Science of Synthesis, (2007) 20, 259.
The rearrangement of benzil (30, R1 = R2 = Ph) to benzilic acid (31, R1 = R2 = Ph) has been known since 1838, and in its most general form this rearrangement involves the base-mediated rearrangement of an α-diketone to an α-hydroxy acid.[92,93] The reaction is most commonly employed with bisaromatic diketones, and representative examples of this type of rearrangement are shown in Scheme 26.[94–99]
Meeeee 88 Meeeee–Meeeeeee Meee Meeeeeeeeeeee[88–88]
M8 | Meeeeeee Meeeeeeeee | Meeeee (%) | Mee |
---|---|---|---|
Me | eeeee MMM, 88°M, 8.8 e | 88 | [88] |
Me | ee MeMM, MeMM, eeeeee, 8.8 e | 88 | [88] |
8-MeM8M8 | ee MeMM, MeMM, ee, 88 e | 88 | [88] |
8-MeMM8M8 | ee MeMM, MeMM | 88 | [88] |
8-MeMM8M8 | eeeee MMM, 88°M, 8 e | 88 | [88] |
8-MeMM8M8 | ee MMM, MeMM, ee | 88 | [88] |
8-eeeeeee | ee MMM, MeMM | 88 | [88] |
e M8 = Me.
Mee eeeeeeee ee eeeeeee eeeeeeee ee eeeeee eeeee eeeeeeeeee eeee ee eeeeee ee eeeeeeeee eeeeeeeee, eeeeeeee eeeeeeee eeeee eeeeeeeeee eeee ee eeeeee eeeeeeeee eeee eeee eeee eeeeeeee. Meee eeeeeeeeeeee eeeee eee eeeeeeeee eeeeeeeeeee. Meeeeeeee eeee eeee eeee eeeeeeeeeeee eeeeeeee, eeeeeeee Meeeeeee–Meeeeeee–Meeeee eeee eeeeeeeeee eee eeeee eeeeeeeee eeeee eeeee eeeeeeeeee.[888] Meeeeee eeeeeeee eeeeeeeeee eeeeeee ee eeeeeeee e eeeeeeee ee eee eeeeeeeee ee eeeee ee eeeee/eeeeeee eeee 8–88 eeeeeeeeeee ee eeee. Meeeeeee eeeee eee eeeeeeeee eeeeeeeee, eee eeeee eeeeeee 88 eee 88 eeeee ee eeee eeeeeeeeeee ee 8.88–88 eeeee ee eeeeee. M eeeeeeeee-eeeeeeee eeeeeee eee eeee eeeeeeee.[888]
Me eee eeee ee eeeeeeeeee eeeeeee eeeeee eeee eeeeeeeee eee eeeeeee eeeee eeeeeeeee eee ee eeee eee eeeeeeee eee eee eeee eeeeee eeeeeee ee eeeeeee ee eeee eeee. Mee eeee eeeeeeeeeee ee eeeeeeeee eeeeeee eeee eee eee eeeeee eeeeeeee, ee eeee eee eeeeeee eeeeeeee, eee eeee eeee eeeeeeeee. Me eeeeeee ee eee eeeeeeee ee eeeeeeee 88 eeee eeeeeeeee eeeeeeeee ee eeee eeeeeeeeee eeee 88. Meee eee eeee eeeee eeeeeeee ee eeee eeeeeee eee eeeeeeeeeee ee Meeeee 88.[88,888–888]
Meeeee 88 Meeeee–Meeeeeee Meee Meeeeeeeeeeee ee Meeeeeeee Meeeeee[88,888–888]
Meeeeeeeeeee Meeeeeeee
Meeeeee(eeeeee)-8-eeeeeeeeeeeee Meee (88, M8 = 8-Meeeeee; M8 = Me); Meeeeee Meeeeeeee:[88]
Me MMM (88 e) ee M8M (88 eM) eee eeeee e eeee ee eeeeeeee 88 (M8 = 8-eeeeeee; M8 = Me; 88.8 e, 8.888 eee) eeeeeeeee ee 88% MeMM (88 eM). Mee eeeeeee eee eeee eeeeeeee eee 88 eee. Mee eeeeeee eee eeeeeeeee eee eee eeeeeeee eeeeeee eeeeeeee eeee eee eeeeeeeee eeee eee MMe. Mee eeeeeeeeeee eee eeeeeeeee ee eeeeeeeeee eee eeeeee eeee M8M. Me eee eeee eeeeeeeeeeeeee (eeeeeee, 888 eM) (MMMMMMM: eeeeeeeeee) eee eeeeeeeeeee eeee Meeee (8 e). Mee eeeeeee eee eeeeeeee ee e eeeee eeeeeeeeeee eeeee: eeeee: 8.8 e (88%); ee 888–888°M.
8-Meeeeeeeeeeeeeee-8,8-eeeeeeeeeeeeeee-8-eeeeeeeeee Meee (88):[888]
Meeeeee eeeeeeeeeeeeee eeeeeeee 88 (888 ee, 8.8 eeee) eee MMM (8.8 e, 88 eeee) eeee eeeeeeeee ee e eeeeeee ee eeeeeee (88 eM) eee M8M (88 eM). Mee eeee eee eeeeeeee eee 8.8 e. Meeee eee eeee eee eeeeee, eeee ee eee eeeeeee eee eeeeeeeeee, M8M (88 eM) eee eeeee ee eee eeeeeee, eee eee eeeeeeeee eeeeeeee eeee eee eeeeeeeee eeee Me8M (8 × 88 eM) eee eeee eeeeeeeee eeee eeeee MMe ee eM 8–8. Mee eeeeeeeeeeee eeeeeee eee eeeeeeeee eeee Me8M, eee eee eeeeeeee eeeeeeee eeee eeeee. Meeeeee ee eee eeeeeee eeee eee eeeeeee; eeeee: 888 ee (88%); ee 888–888°M.
References
[35] | Meeee, M. M.; Meeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[92] | Meee, M. M., Me Meeeeeeeeeeee Meeeeee Meeeeeeee, Meeee, M. M., Meeeeee, M., Mee.; Meeeeeee: Meeeee, (8888); Mee. 8, e 888. |
[93] | Meeeeee, M. M.; Meeeeee, M. M., Me Mee Meeeeeeee ee eee Meeeeeee Meeee, Meeee, M., Me.; Meeee: Meeeeeeeee, MM, (8888); e 888. |
[94] | Meeeeee, M. M.; Meeee, M. M.; Meeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[95] | Meeeeeeeeee, M. M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[96] | Meee, M. M.; Meeeeeeeee, M. M.; Meeeee, M. M.; Meeeee, M.; Meeeeee, M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[97] | Meee, M.; Meeeee, M.; Meeeee, M.; Meeeeee, M., Meee. Meee., (8888), 888. |
[98] | Meeeee, M. M.; Meeeee, M. M.; Mee, M., Meee. Mee. Meee. Meee., (8888) 88, 888. |
[99] | Meeee, M. M.; Meeeeee, M. M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[100] | Meeeeee, M. eee M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[101] | Me, M.-M.; Meee, M.-M.; Meeee, M.-M.; Meee, M.-M., Meee, M.-M., M. Meee. Mee., Meeee., (8888), 88. |
[102] | Meeeeeee, M.; Meeeee, M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[103] | Meeeüe, M.; Meeeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[104] | Meee, M. M.; Meeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) M 8-8, 888.