Disaccharide formation using unprotected 2-acetamido sugars as donors, and unprotected glycosides as acceptorsa.
| Entry | Donor | Acceptor | Product | Isolated yield of (1→6) linked disaccharide (%) | Regioselectivity/total combined yield |
|---|---|---|---|---|---|
| 1 | GlcNAc 2a |
|
|
49 | (1→6) only |
| 2 | GlcNAc 2a |
|
|
46 | (1→6) only |
| 3 | GlcNAc 2a |
|
|
25 | 3 regioisomers/50% |
| 4 | GlcNAc 2a |
|
|
40e | (1→6) onlye |
| 5 | GlcNAc 2a |
|
|
36 | 3 regioisomers/48% |
| 6 | GlcNAc 2a |
|
|
33 | 3 regioisomers/55% |
| 7 | GlcNAc 2a |
|
|
32a | 2 regioisomers/46%a |
| 44b | (1→6) onlyb | ||||
| 8 | GlcNAc 2a |
|
|
39e | (1→6) onlye |
| 9 | GlcNAc 2a |
|
|
31a | 3 regioisomers/62%a |
| 37d | 3 regioisomers/54%d | ||||
| 10 | GlcNAc 2a |
|
|
39a | 3 regioisomers/68%a |
| 26b | 3 regioisomers/52%b | ||||
| 11 | GlcNAc 2a |
|
|
45 | (1→6) < 1% of any other regioisomer |
| 12 | GlcNAc 2a |
|
|
34a | 3 regioisomers/47%a |
| 39b | 3 regioisomer/58%b | ||||
| 13 | GlcNAc 2a |
|
|
18 | 3 regioisomers/51% |
| 14 | GalNAc 2b |
|
|
40 | (1→6) only |
| 15 | GalNAc 2b |
|
|
26a | 2 regioisomers/40%a |
| 30c | (1→6) onlyc | ||||
| 16 | ManNAc 2c |
|
|
15 | (1→6)/trace amount of another regioisomer |
Reaction conditions: (i) DMC 1, Et3N, H2O, 0 °C, 1 h, then freeze-dry; acceptor (3a–i or 5d), MeCN/DMF (10 : 1), 4 Å powdered molecular sieves, TsOH, rt, 3 h.
Reaction performed at 0 °C.
Reaction performed at −10 °C.
Reaction performed at −16 °C for 24 h.
Reaction performed in DMF as solvent.