Controllable highly stereoselective reaction of in situ generated magnesium dienolate intermediates with different electrophiles.
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.
Lu
Zhan
Z
Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, People's Republic of China.
Chai
Guobi
G
Zhang
Xiaobing
X
Ma
Shengming
S
D000215:Acylation; D000478:Alkylation; D002384:Catalysis; D018360:Crystallography, X-Ray; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry; D008274:Magnesium / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
D004952:Esters; D005290:Ferric Compounds; D009942:Organometallic Compounds; D008274:Magnesium