Table 2.
Tandem Michael-Henry reaction between 1,2-diones and nitroalkenesa
![]() | |||||||
|---|---|---|---|---|---|---|---|
| entry | R1 | R2 | R3 | R4 | drb | yield (%)c | eed (%) |
| 1 | -(CH2)3- | H | Ph(3a) | 88:12 | 75 | 97 | |
| 2 | -(CH2)3- | H | 4-MeC6H4(3b) | 92:8 | 83 | 97 | |
| 3 | -(CH2)3- | H | 4-MeOC6H4(3C) | 88:12 | 82 | 97 | |
| 4 | -(CH2)3- | H | 4-ClC6H4(3d) | 86:14 | 68 | 96 | |
| 5 | -(CH2)3- | H | 4-BrC6H4(3e) | 94:6 | 89 | 97 | |
| 6 | -(CH2)3- | H | 4-CNC6H4(3f) | 91:9 | 79 | 97e | |
| 7 | -(CH2)3- | H | 4-NO2C6H4(3g) | 94:6 | 90 | 93e | |
| 8 | -(CH2)3- | H | 2-MeOC6H4(3h) | 95:5 | 87 | 94 | |
| 9 | -(CH2)3- | H | 2-BrC6H4(3i) | 72:28 | 66 | 92 | |
| 10 | -(CH2)3- | H | 3-ClC6H4(3j) | 88:12 | 77 | 96e | |
| 11 | -(CH2)3- | H |
|
92:8 | 89 | 99e | |
| 12 | -(CH2)3- | H | n-C6H13(3l) | 88:12 | 77 | 97 | |
| 13 | -(CH2)3- | Me | Ph (3m) | 88:12 | 67f | 97 | |
| 14 | Me | H | H | Ph | --- | 0 | --- |
| 15 | -(CH2)2- | Me | Ph | --- | 0g | --- | |
All reactions were conducted with trans-nitroalkenes (0.25 mmol), 1,2-diones (0.30 mmol), and catalyst 4 (15 mmol %) in toluene (1.5 mL) at room temperature for 26 to 32 h (TLC monitoring).
Diastereomeric ratio was determined by 1H NMR analysis of the crude mixture.
Yield of the isolated major diastereomer after column chromatography.
Unless otherwise specified, ee values were determined by HPLC analysis on a ChiralCel OJ-H column.
Determined by HPLC analysis on a ChiralPak AD-H column.
The reaction time was 72 h.
A complex mixture of unidentified products was obtained.
