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Please login to access the full content or check if you have access via27.24.3.1.1.1 Variation 1: (Triphenylphosphoranylidene)thioketene and -ketenimines, and Allenylidene Ylides by Addition to 1,1-Dichloro(hetero)alkenes
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Schobert, R.; Gordon, G. J., Science of Synthesis, (2004) 27, 1043.
Phosphacumulene ylides 141 are prepared in good yields by the reactions of (methylene)triphenylphosphorane with geminal dihalides 140 (Scheme 50). The reactions, which require a (methylene)triphenylphosphorane to dihalide stoichiometry of 3:1 proceed via the corresponding phosphonium salts. These intermediates undergo rapid tandem transylidation–dehydrohalogenations with excess starting (methylene)triphenylphosphorane, to afford (phosphoranylidene)ketenimines 141 (X = NR1) with 1,1-dichloroimines 140 (X = NR1; Y = Cl),[52] (phosphoranylidene)thioketene ylide 141 (X = S) from reactions with thiophosgene 140 (X = S; Y = Cl),[52] and (allenylidene)triphenylphosphoranes 141 (X = CR1R2) from reactions with electron-poor 1,1-dihaloalkenes 140 (X = CR1R2; Y = Cl, Br).[561] However, the ylide 141 (X = O) cannot be prepared by a reaction of (methylene)triphenylphosphorane with phosgene.[259]
Meeeee 88 Meeeeeeeeeeeeee Meeeee eeee (Meeeeeeee)eeeeeeeeeeeeeeeeeeee eee Meeeeee Meeeeeeee[88,888]
| M | M | Meeee (%) ee 888 | ee (°M) | MM (ν̃ ee−8) | 88M MMM (δ) | Mee |
|---|---|---|---|---|---|---|
| MMe | Me | 88 | 888–888 | 8888 | 8.88 | [88] |
| MMe | Me | 88 | 888–888 | 8888 | 8.88 | [88] |
| MMe | Me | 88 | 888–888 | 8888 | 8.88 | [88] |
| MM8M8-8-Me | Me | 88 | 888 | 8888 | 8.88 | [88] |
| MM8M8-8,8-Me8 | Me | 88 | 888 | 8888 | 8.88 | [88] |
| M-8-Mee | Me | 88 | 88–88 | 8888 | 8.88 | [88] |
| M | Me | 88 | 888–888 | 8888, 8888 | −8.88 | [88] |
| M(MM)(MM8Me) | Me | 88 | 888 | 8888 | 8.88 | [888] |
| eeeeeeee-8,8′-eeee | Me | 88 | 888 | 8888 | −8.88 | [888] |
Meeeeeeeeeee Meeeeeeee
Meeeeeeeeeeeeeeeeeeeeeeeeeee 888 (M = MM8) eeee 8,8-Meeeeeeeeeeeee; Meeeeee Meeeeeeee:[88]
MMMMMMM: Meeeeee ee e eeeeeeeeee; eeeeeee, ee eee ee eeeeeeee ee eeeeeee eeee eeeeee eeeeee eeee eee eeeee.
M Me eeee eeee eeee ee (eeeeeeeee)eeeeeeeeeeeeeeeeeeee (88.8 e, 88.8 eeee) (eee eeeeeeeeeee eee Meeeeee 88.88.8.8.8.8) ee eeeee eeeeeee/MMM (8:8; 888 eM) eeeee eee M8 eee eeeeeee ee 8°M eee eeeeeee eeeeeeee eeee ee M-eeeeeeeeeee 8,8-eeeeeeeeeeeee (88.8 eeee) ee eeeeeee (88 eM). Meeee e eeeeeee eeee ee eeeeeeee, eee eeeeeee eee eeeeeeee eeeee M8 eeeeeee e Meeeeee-eeee eeeeee eeeeee ee eeeeee eeeeeeeee eeeeee(eeeeeeeee)eeeeeeeeeee eeeeee. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeeeeee (eeeee MeMMe, ee MeMMe/Me8M, ee MeMMe/eeeeeee).
References
| [52] | Meeeeeee, M. M.; Meeeee, M., Meee. Mee., (8888) 888, 8888. |
| [259] | Meeeeeee, M. M., Meeee. Meee., (8888) 88, 888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 888. |
| [561] | Meeeeeee, M. M.; Meeeee, M., Meeeeeeeeee Meee., (8888), 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 8, 888.
- 8.Meeeee-Meee, (8888) M 88-8, 8888.
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