Stereoselective free-radical addition of secondary phosphine selenides to aromatic acetylenes

作者：Trofimov Boris A^*; Gusarova Nina K; Arbuzova Svetlana N; Ivanova Nina I; Artem'ev Alexander V; Volkov Pavel A; Ushakov Igor' A; Malysheva Svetlana F; Kuimov Vladimir A

来源：Journal of Organometallic Chemistry, 2009, 694(5): 677-682.

DOI：10.1016/j.jorganchem.2008.11.043

• Free-radical addition
• Secondary phosphine selenides
• Acetylenes
• Microwave activation

Free-radical addition (AIBN, 65-70 degrees 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.

• 出版日期2009-3-1