Stereoselective free-radical addition of secondary phosphine selenides to aromatic acetylenes
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- 作者：Boris A. Trofimov ; Nina K. Gusarova ; Svetlana N. Arbuzova ; Nina I. Ivanova ; Alex ; er V. Artem’ ; ev ; Pavel A. Volkov ; Igor’ ; A. Ushakov ; Svetlana F. Malysheva ; Vladimir A. Kuimov
- 关键词：Free-radical addition ; Secondary phosphine selenides ; Acetylenes ; Microwave activation
- 刊名：Journal of Organometallic Chemistry
- 出版年：2009
- 出版时间：1 March 2009
- 年：2009
- 卷：694
- 期：5
- 页码：677-682
- 全文大小：596 K
文摘
Free-radical addition (AIBN, 65–70 °C, 5–7 h) of secondary phosphine selenides to arylacetylenes proceeds stereoselectively to give anti-Markovnikov adducts of predominantly Z-configuration (up to 97 % ) in 60–80 % isolated yields, thus representing a rare example of stereoselective free-radical addition to the triple bond. Microwave irradiation (600 W) of the reactants with the same content of AIBN reduces the reaction time to 8 min though compromises the stereoselectivity. Under UV-initiation the reaction loses its stereoselectivity due to isomerization of the primary Z-adducts. In this reaction, a specific facilitating and Z-configuration-controlling effect of aromatic substituents at the triple bond has been revealed.