Ogata Akitoshi, Nemoto Masami, Kobayashi Kenji, Tsubouchi Akira, Takeda Takeshi
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
J Org Chem. 2007 May 11;72(10):3816-22. doi: 10.1021/jo070149u. Epub 2007 Apr 13.
The stereoselective alkenylation of unsaturated compounds by means of a (Z)-alkenyl sulfone-titanocene(II) system is described. Treatment of alkynes and (Z)-alkenyl methyl sulfones with the titanocene(II) reagent Cp2Ti[P(OEt)3]2 produced conjugated dienes. This alkenylation system is also applicable to polar C=O bonds; the simple mixing of carbonyl compounds, (Z)-alkenyl methyl sulfones, and the titanocene(II) reagent formed allylic alcohols. The advantages of alkenylation are that it requires no prepreparation of the alkenylmetal reagent and that it proceeds with complete stereoselectivity.
描述了通过(Z)-烯基砜-二茂钛(II)体系对不饱和化合物进行立体选择性烯基化反应。炔烃和(Z)-烯基甲基砜与二茂钛(II)试剂Cp2Ti[P(OEt)3]2反应生成共轭二烯。该烯基化体系也适用于极性C=O键；羰基化合物、(Z)-烯基甲基砜和二茂钛(II)试剂简单混合即可生成烯丙醇。烯基化反应的优点是无需预先制备烯基金属试剂，并且反应具有完全的立体选择性。
