Table 2.
O - and C-Mannosylation with Donor 13.
| Entry | Nucleophile | Equiv (M conc) | β-gly/cycl | α-gly/cycl |
|---|---|---|---|---|
|
| ||||
| 37/(28+29)c | 38/(28+29)c | |||
| 1a | iPrOH | 0.8 (0.014) | 2.17 | 0.15 |
| 2a | iPrOH | 1.2 (0.020) | 3.66 | 0.28 |
| 3a | iPrOH | 1.5 (0.026) | 5.36 | 0.44 |
| 4a | iPrOH | 2.5 (0.043) | 10.99 | 0.99 |
| 5a | iPrOH | 3 (0.051) | 13.09 | 1.28 |
| 6a | iPrOH | 4 (0.068) | 15.75 | 1.14 |
| 7a | iPrOH | 5 (0.085) | 19.38 | 1.53 |
| 8a | iPrOH | 8 (0.136) | 24.34 | 1.60 |
| 39/(28+29)c | - | |||
| 9b | TMSCH2C(Me)=CH2 | 2 (0.034) | 0.06 | - |
| 10b | TMSCH2C(Me)=CH2 | 4 (0.068) | 0.18 | - |
| 11b | TMSCH2C(Me)=CH2 | 8 (0.136) | 0.40 | - |
| 12b | TMSCH2C(Me)=CH2 | 12 (0.204) | 0.55 | - |
| 13b | TMSCH2C(Me)=CH2 | 15 (0.255) | 0.69 | - |
| 14b | TMSCH2C(Me)=CH2 | 20 (0.34) | 0.87 | - |
| 15b | TMSCH2C(Me)=CH2 | 30 (0.51) | 1.40 | - |
a
Experimental conditions: TTBP (4 equiv), 1-octene (10 equiv), molecular sieves 4 Å, Tf2O (1.2 equiv) at −72 °C;
b
Experimental conditions: TTBP (4 equiv), molecular sieves 4 Å, Tf2O (1.2 equiv) at − 72 °C;
c
Molar ratios were determined by UHPLC/UV/MS