𝔖 Bobbio Scriptorium
✦   LIBER   ✦

The C- and D-ring problems of sterol biosynthesis: hydride shift versus carboncarbon bond migration due to conformational changes controlled by counteranion

✍ Scribed by Mugio Nishizawa; Arpita Yadav; Hiroshi Imagawa; Takumichi Sugihara


Publisher
Elsevier Science
Year
2003
Tongue
French
Weight
529 KB
Volume
44
Category
Article
ISSN
0040-4039

No coin nor oath required. For personal study only.

✦ Synopsis


The first calculations of a C-ring model cation of sterol biosynthesis in the presence of selected counteranions have been performed. [TiCl 4 OH] -ion significantly stabilizes the perpendicular cation conformer that leads to carbon carbon bond migration and formation of a six-membered ring secondary cation. The [TiF 4 OH] -ion, however, stabilizes the parallel cation conformer that leads to hydride shift as observed indeed.