Table 2.
One‐pot/two‐step modular double addition of different organolithium or organomagnesium reagents to benzonitrile (1a) under air, at room temperature and in the absence of any additional solvent.[a]
|
| ||||||
|---|---|---|---|---|---|---|
|
Entry |
R1Li[b] |
Equiv. |
3a,n–q [%][c] |
R2Li[b] |
Equiv. |
4a–j [%][c] |
|
1 |
MeLi |
1 |
3a (99) |
n‐BuLi |
1 |
4a (52) |
|
2 |
MeLi |
1 |
3a (99) |
n‐BuLi |
2 |
4a (56) |
|
3 |
MeLi |
1 |
3a (99) |
n‐BuLi |
3 |
4a (68) |
|
4 |
MeLi |
1 |
3a (99) |
EtLi |
3 |
4b (52) |
|
5 |
EtLi |
2 |
3n (79) |
n‐BuLi |
3 |
4c (38) |
|
6 |
EtLi |
2 |
3n (79) |
MeLi |
3 |
4b (45) |
|
7 |
n‐BuLi |
2 |
3o (86) |
MeLi |
3 |
4a (66) |
|
8 |
n‐BuLi |
2 |
3o (86) |
EtLi |
3 |
4c (74) |
|
9 |
MeLi |
1 |
3a (99) |
TMSCH2Li |
3 |
4d (52) |
|
10 |
EtLi |
2 |
3n (79) |
TMSCH2Li |
3 |
4e (76) |
|
11 |
n‐BuLi |
2 |
3o (86) |
TMSCH2Li |
3 |
4f (54) |
|
12 |
MeLi |
1 |
3a (99) |
ThienLi |
3 |
4g (56) |
|
13 |
EtLi |
2 |
3n (79) |
ThienLi |
3 |
4h (51) |
|
14 |
n‐BuLi |
2 |
3o (86) |
ThienLi |
3 |
4i (65) |
|
15 |
ThienLi |
1 |
3q (84) |
MeLi |
3 |
4g (55) |
|
16 |
ThienLi |
1 |
3q (84) |
EtLi |
3 |
4h (30) |
|
17 |
ThienLi |
1 |
3q (84) |
n‐BuLi |
3 |
4i (24) |
|
18 |
MeLi |
1 |
3a (99) |
i‐PrMgCl2Li |
3 |
4j (25) |
[a] General conditions: reactions performed under air/moisture, at room temperature and in the absence of external organic solvents, using 0.5 mmol of benzonitrile (1a). [b] Commercial solution of MeLi (1.6 M in diethyl ether), EtLi (0.5 M in benzene/cyclohexane), n‐BuLi (2.5 M in hexanes), TMSCH2Li [TMS=(CH3)3Si; 1 M in pentane], ThienLi (Thien=2‐thienyl; 1 M in THF/hexanes), and i‐PrMgCl2Li (1.3 M in THF) were employed. [c] Yields determined by 1H NMR using trimethoxybenzene as internal standard (0.5 mmol) (see Supporting Information).