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Please login to access the full content or check if you have access via Variation 2: Reduction of Titanium(IV)–Chloro Complexes by Sodium Amalgam in the Presence of Alkenes or Alkynes

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032541.

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.

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