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Controllable highly stereoselective reaction of in situ generated magnesium dienolate intermediates with different
Zhan Lu1, Guobi Chai, Xiaobing Zhang
1Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, People's Republic of China.
Abstract:
In this paper, we have described an efficient controllable stereoselective alpha-acylation and -allylation reaction of the magnesium dienolate intermediates generated in situ from the Fe(III)-catalyzed reaction between 2,3-allenoates and Grignard reagents with different electrophiles to afford 2-acylated or allylated 3( Z)- or ( E)-alkenoates depending on the nature of the electrophiles and reaction conditions. The distinct stereoselectivity may be caused by the isomerization of metallic Z-1,3-dienoate to E-1,3-dienoate via the intermediacy of anti-allylic MgCl and syn-metallic species.
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