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Please login to access the full content or check if you have access via2.10.9.2.2 Variation 2: Reduction of Titanium(IV)–Chloro Complexes by Sodium Amalgam in the Presence of Alkenes or Alkynes
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Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 541.
The reduction of sterically bulky [TiCl2(OAr1)2] (185, Ar1 = 2,6-Ph2C6H3, 2,3,5,6-Ph4C6H) complexes with sodium amalgam in the presence of hex-3-yne afforded titanacyclopentadienes 187 (Scheme 93).[314] Treatment of titanacyclopentadiene 187 with but-1-ene gives titanacyclopentane 188. Diphenyl-substituted titanacyclopentane 189 could be prepared directly from 185, styrene, and sodium amalgam (Scheme 93).[315] Reactions of styrene-derived titanacyclopentanes 189 with alkynes afford the corresponding titanacyclopentadienes by ligand exchange. This method is also effective for the preparation of bis(η5-cyclopentadienyl)titanacycles 190 and 173 (Scheme 93). The cyclization of many types of diynes[316,317] and enynes[318] can proceed by this method.
Meeeee 88 Meeeeeeeeee ee Meeeeeeeeeee eeee Mee(eeeeeee)eeeeeeeeeeeeeeee(MM) ee Meeeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM) eee Meeeeeeeeee Meeeeeeeeeee ee eee Meeeeeee ee Meeeee Meeeeee[888–888]
| M8 | M8 | (M)e | Meeeee (%) | Mee |
|---|---|---|---|---|
| Me | Me | (MM8)8 | 88 | [888] |
| Me | Me | (MM8)8 | 88 | [888] |
| Me | Me | (MM8)8 | 88 | [888] |
| Me | Me | (MM8)8 | 8 | [888] |
| Me | Me | (MM8)8 | 88 | [888] |
| Me | eMe | (MM8)8 | 88 | [888] |
| Me | Me | (MM8)8 | 88 | [888] |
| MMe | MMe | (MM8)8 | 88 | [888] |
| Me | Me | M | 88 | [888] |
e Mee eeeee ee eeeee ee eee eeeee eeeeeee eeeeeeeee eeee eeeeeeeeee ee eeeeeee 888.
Meeeeeeeeeee Meeeeeeee
(8,8-Meeeeeeeeee-8,8-eeee-8,8-eeee)eee(8,8-eeeeeeeeeeeeeee)eeeeeeee(MM) (888, Me8 = 8,8-Me8M8M8); Meeeeee Meeeeeeee:[888]
M eeeeeee ee 888 (Me8 = 8,8-Me8M8M8; 8.8 e 8.88 eeee) eee eee-8-eee (8.88 eM, 8.88 eeee) ee eeeeeee (88 eM) (MMMMMMM: eeeeeee ee eeeeeeeeeeee!) eee eeeeeee eeee e Me (8.88 e, 8.88 eeee) eeeeeee eee 88 e. Mee eeeeeeeee eeee eee eeee eeeeee eeee eeeeee eeeeee 8 e eee eeeeeee eeeeee e eeee eeeeee eeeee. Mee eeeeeeeeee eee eeeeeeee eeee eee Me eeee, eeeeeeee, eee eeeeeeeeee ee eeeee ee eeeee eee eeeee eeeeeee, eeeee eee eeeeeeeeeee ee e eeeeeee eeeeee ee eeeeeee. Mee eeee eee eeeeee eeeeee ee eeeeee eeeeee ee eeeeee eee eeeeeeeee ee eeeeee eeeeeeee, eeeee eeee eeeeee eeee e eeeee eeeeee ee eeeeeee eee eeeee eeeee eeeeee; eeeee eee eeeee; MM-MM e/e: 888 (M+); 8M MMM (eeeeeee-e8, 88°M, δ): 8.8–8.8 (eeeeeeeee), 8.88 (e), 8.88 (e, MM8Me), 8.88 (e), 8.88 (e, MM8Me); eeeeeeee 88M MMM (eeeeeee-e8, 88°M, δ): 888.8 (MeMMe), 888.8 (MeMM), 888.8 (MeMMeMMe), 88.8, 88.8 (MM8Me), 8.88, 88.8 (MM8Me).
References
| [314] | Meee, M. M.; Meeeeee, M. M.; Meeeeee, M. M.; Meeeeeee, M. M., Meeeeeeeeeeeeee, (8888) 88, 8888. |
| [315] | Meeeeee, M. M.; Meeeeee, M. M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [316] | Meeeee, M. M.; Meeeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [317] | Meeeee, M. M.; Meeee, M. M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [318] | MeeeeMeee, M. M.; Meeeee, M. M.; Meeee, M. M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88/8, 888.
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