Dual reactivity of secondary phosphines and their chalcogenides towards 1-(vinyloxy)alkylferrocenes: the switch between alpha- and beta-addition

作者：Artem'ev Alexander V; Oparina Ludmila A; Gusarova Nina K; Vysotskaya Oksana V; Tarasova Olga A; Gatilov Yuriy V; Albanov Alexander I; Trofimov Boris A^*

来源：Tetrahedron, 2015, 71(13): 1998-2003.

DOI：10.1016/j.tet.2015.02.011

• Addition
• Enol ethers
• Ferrocene
• Regioselectivity
• Phosphines

The secondary phosphines and their sulfides regioselectively add, under free radical conditions (AIBN, 65 degrees C or UV-irradiation, rt), to (vinyloxy)methyl- and 1-(vinyloxy)ethylferrocenes to give anti-Markov-nikov adducts in high yields. Without any initiator, the secondary phosphine selenides, when reacted with the above alkenes (rt, 24 h), selectively form Markovnikov adducts, which readily decompose upon handling to afford diorganyl[1-(ferrocenyl)alkyl]phosphine selenides, R2P(Se)CH(R')Fc (R=Ph; R'=H or Me) in 28-39% isolated yields. The synthesized compounds were characterized using H-1, C-13, P-31 NMR, and FTIR spectroscopy as well as X-ray diffraction analysis.

• 出版日期2015-4-1