Table 3. Summary of Kinetic Reaction Profiles Derived from Solvent Screening Studiesa.
entry | solvent | t (h)b | 4b yield (%) | dehydration: 4c + 4d + 4e yield (%) | carbon mass balance (%) | cis–trans ratio 4b |
---|---|---|---|---|---|---|
1 | water | 0.5 | 49 | 40 | 89 | 64:36 |
2 | MeOH | 0.75 | 46 | 34 | 80 | 65:35 |
3 | EtOH | 0.75 | 56 | 36 | 92 | 67:33 |
4 | n-PrOH | 1.5 | 61 | 28 | 89 | 67:33 |
5 | i-PrOH | 2 | 69 | 27 | 96 | 71:29 |
6 | n-BuOH | 1 | 36 | 53 | 89 | 69:33 |
7 | i-BuOH | 3 | 61 | 25 | 86 | 68:32 |
8 | s-BuOH | 3 | 72 | 22 | 94 | 67:33 |
9 | t-BuOH | 3 | 74 | 21 | 95 | 67:33 |
10 | EtOAc | 4 | 62 | 37 | 99 | 69:31 |
11 | CPME | 2 | 62 | 36 | 98 | 69:31 |
12 | THF | 7 | 65 | 31 | 96 | 71:29 |
13 | dioxane | 2 | 69 | 29 | 98 | 68:32 |
14c | toluene | 7 | 26 | 73 | 99 | 71:29 |
15c | heptane | 7 | 29 | 69 | 98 | 52:48 |
Reaction conditions: 50 mmol of 4 and 5.1 wt % Ru/C, 100 °C, 50 bar H2.
Specific reaction time upon which complete conversion was observed via GC-FID.
The reaction was run for 7 h without collection of kinetic samples. Since the diol products emulsified out of the solvent, the entire reaction mixture was dissolved in acetonitrile for GC analysis.