The C-ring problem of sterol biosynthesis: TiCl(4)-induced rearrangement into the anti-Markovnikov cation corresponding to the C-ring.
[reaction: see text] Cation 9, generated by the reaction of diol 8 and BF(3).Et(2)O, SnCl(4), Sc(OTf)(3), FeCl(3), TiF(4), or CF(3)SO(3)H, leads to a hydride shift, providing cation 11, which corresponds to the initiation of backbone rearrangement. On the other hand, TiCl(4) selectively induces rearrangement to secondary cation 13 by ring expansion, which corresponds to the C-ring formation of sterol biosynthesis. AlCl(3) and ZrCl(4) induce further rearrangement into six-membered ring tert-cation 16.
Nishizawa
M
M
Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Japan. mugi@ph.bunri-u.ac.jp
Iwamoto
Y
Y
Takao
H
H
Imagawa
H
H
Sugihara
T
T
D002412:Cations; D018716:Molecular Mimicry; D015394:Molecular Structure; D013261:Sterols / Q000096:biosynthesis / Q000138:chemical synthesis*; D014025:Titanium / Q000737:chemistry
D002412:Cations; D013261:Sterols; C025096:titanium tetrachloride; D014025:Titanium