Table 6.
Double in situ Generation of Ketenes.a

| entry | catalyst (mol%) | R1 | R2 | R3 | % yieldb | % eec | Z:E d | 3 |
|---|---|---|---|---|---|---|---|---|
| 1 | MeQd (10) | Me | Me | Ph | 61 | 91 | >97:3 | (−)e-3a |
| 2 | MeQd (2.5) | Me | Me | Ph | 74 | 92 | 99:1 | (−)e-3a |
| 3 | TMSQ (10) | Me | Me | Ph | 67 | 93 | 99:1 | (+)e-3a |
| 4 | MeQd (10) | Me | Et | Ph | 48 | 95 | 78:22 | (−)-3b |
| 5 | MeQd (10) | Et | Me | Ph | 71 | 97 | 98:2 | (−)-3e |
| 6 | MeQd (10) | Et | Et | Ph | 35 | 97 | 86:14 | (−)-3f |
| 7 | MeQd (10)f | Me | Ph | Et | 41 | >99 | 33:67 | E-(−)-3p |
Only one heterodimer regioisomer observed in all cases by GC-MS analysis of crudes and NMR analysis of 3.
Isolated yield for both isomers.
ee determined by chiral HPLC.
Z:E ratio determined by GC-MS analysis.
Sign of specific rotation; (+)-enantiomer or (−)-enantiomer.
Reaction conducted in the presence of 2 equiv LiClO4.