Table 1.
Alkylation of dihydroperoxide 1a
| |||
|---|---|---|---|
| entry | electrophile | methoda | product (yield) |
| 1 | n-C10H21I | A | 2a (93%) |
| 2 | n-C10H21I | C | 2a (19%)b,c |
| 3 | n-C10H21I | D | 2a (7%) b,c |
| 4 | n-C10H21Br | A or F | - |
| 5 | n-C10H21I | E | - |
| 7 | n-C6 H13I | A | 2b (79%) |
| 8 | BnBr | A | 2c (56%) |
| 9 |
|
A | 2d (79%) |
| 10 |
|
B | 2d (80%) |
| 11 | Ph(CH2)4–OTf | B | 2e (68%) |
| 12 | 2-iodooctane | A | - |
| 13 | 2-iodooctane | C | 2f (trace)c |
| 14 |
|
B | 2f (53%) |
| 15 |
|
B | 2g (42%) |
| 16 | t-BuBr | A | monoalkylation (35%) |
| 17 | t-BuBr | G | NR |
| 18 | t-BuBr | H | -c |
A: Ag2O, RBr or RI, EtOAc; B: KOtBu, ROTf, THF; C: CsOH•H2O (2 equiv), RI (2 eq) DMF; D: CsCO3 (2 equiv), RI (2 equiv), DMF; E: KOtBu (2.1 equiv), RI (2 equiv), THF; F: 50% KOH (4 equiv), RBr (2 equiv), n-Bu4NBr (10%), cyclohexane, 50 °C; G: K2CO3, acetone; H: K2CO3,DMF, 70 °C.
NMR-based yield (internal standard).
Decomposition of 1a with formation of ketone.