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  • Selective preparation of benzyltitanium compounds by the metalative Reppe Reaction. Its application to the first synthesis of alcyopterosin A.
    Journal of the American Chemical Society, 2002
    Co-Authors: Ryoichi Tanaka, Yoshitaka Nakano, Daisuke Suzuki, And Hirokazu Urabe, Fumie Sato
    Abstract:

    Dialkoxytitanacyclopentadienes, prepared from two different acetylenes and a divalent titanium alkoxide reagent, Ti(O-i-Pr)4/2 i-PrMgCl, reacted with propargyl bromide to give directly benzyltitanium compounds. The resultant benzyltitanium compounds underwent deuteriolysis, iodinolysis (with I2), or oxygenation (with O2 gas) to give the corresponding deuterium-labeled compounds, iodides, or alcohols, illustrating their synthetic versatility. The first synthesis of alcyopterosin A, a bicyclic aromatic sesquiterpenoid recently isolated and characterized, has been achieved by this method, starting with an appropriate combination of an acetylene and a diyne.