Table 1:
| ||||
---|---|---|---|---|
Entry | Diazirine | Additive | Ɛ[e] | T1 [s] [f] |
| ||||
1 | none | _[g] | n/a | |
2[b] | pyridine | 3500 | 168 ± 18 | |
3[c] | MeCN | 3400 | 179 ± 16 | |
4[d] | D2O | 11200 | 176 ± 3 | |
5 | none | _[g] | n/a | |
6[b] | pyridine | 6000 | 215 ± 22 | |
7[c] | MeCN | 3200 | 172 ± 17 | |
8[d] | D2O | 1900 | 234 ± 28 | |
9 | none | _[g] | n/a | |
10[b] | pyridine | 16 000 | 141 ± 4 | |
11 [c] | MeCN | 1000 | 263 ± 83[h] | |
12[d] | D2O | 2500 | 164 ± 25 |
Conditions for all experiments: diazirines 2–4 (12.5 mm) and Ir precatalyst B (125 μm) in [D4]MeOH. See the Supporting Information for more details on the hyperpolarization method.
Pyridine (1.00 mm, 8 equiv with respect to B).
Acetonitrile (1.00 mm).
D2O (925 mm).
Signal enhancement measured at 8.45 T and calculated by comparison to a reference of neat 15N-acetonitrile.
T1 measured at 1 T. See the Supporting Information for measurements at other fields.
No hyperpolarized signal observed.
The low signal enhancement and volatility of acetonitrile contribute to the larger T1 error. n/a=not applicable.