分子内シリル基移動を利用した共役アルキン類の新規連続的活性化法の開発

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  • Development of a New Method for Consecutive Activation of Conjugated Alkynes Based on Intramolecular Silyl Migration
  • ブンシナイ シリルキ イドウ オ リヨウシタ キョウヤク アルキンルイ ノ シンキ レンゾクテキ カッセイカホウ ノ カイハツ

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  A new method for consecutive α- and β-activation of propiolates toward electrophiles has been developed, which is mediated by suitable tertiary amines (e.g., DABCO) involving intramolecular silyl migration as a key step. Methyl 3-trimethylsilylpropiolate was reacted with aromatic aldehyde in the presence of DABCO in refluxing benzene to give a highly functionalized olefin product, in which new carbon-carbon bonds were formed at both α- and β-positions of the starting propiolate. On the other hand, when using aliphatic aldehyde the reaction course was dramatically changed to afford a propargyl TMS ether as a sole product. However, we suppose that these reactions have a common reaction pathway partly, including ammonium ylide-alkylidene carbene equilibrium, and that the former products arise from the ylide form and the latter from the carbene form. These domino reactions were successfully applied for an intramolecular version by use of substrates having both formyl group and TMS-propiolate structure derived from salicylaldehyde, leading to a new formylcoumarin-forming reaction.<br>

収録刊行物

  • 薬学雑誌

    薬学雑誌 127 (8), 1207-1213, 2007-08-01

    公益社団法人 日本薬学会

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