Diastereoselective Iodocarbocyclization Reaction of 2- or 3-Oxy-4-pentenylmalonate Derivatives.
1,2- Or 1,3-asymmetric induction in the iodocarbocyclization reaction of 4-pentenylmalonate derivatives having a stereogenic center at an allylic or a homoallylic position has been investigated. The iodocarbocyclization reactions of 3-oxy-4-pentenylmalonate derivatives proceeded with high cis-selectivity through stereoelectronic control of the oxygenated substituent at an allylic position. In the reaction of (S)-2-siloxy-4-pentenylmalonate, an excellent diastereoselectivity was achieved through the utilization of double stereodifferentiation with a chiral titanium catalyst. Furthermore, as an application of the present reaction, the asymmetric syntheses of cyclosarkomycin and a synthetic intermediate of brefeldin A from optically pure 2- and 3-oxy-4-pentenylmalonate derivatives are also described.
Inoue
Tadashi
T
Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-03, Japan.
Kitagawa
Osamu
O
Oda
Yoko
Y
Taguchi
Takeo
T