On the mechanism of base-induced rearrangements of epoxides to ketones: a formal synthesis of (S)-physoperuvine

Authors
Hodgson, DM Robinson, LA Jones, ML
Citation
Dm. Hodgson et al., On the mechanism of base-induced rearrangements of epoxides to ketones: a formal synthesis of (S)-physoperuvine, TETRAHEDR L, 40(49), 1999, pp. 8637-8640
Citations number
18
Categorie Soggetti
Chemistry & Analysis","Organic Chemistry/Polymer Science
Journal title
TETRAHEDRON LETTERS
ISSN journal
00404039 → ACNP
Volume
40
Issue
49
Year of publication
1999
Pages
8637 - 8640
Database
ISI
SICI code
0040-4039(199912)40:49<8637:OTMOBR>2.0.ZU;2-G
Abstract
The enantioselective alpha-deprotonation-rearrangement of trans- and cis-5- silyloxycycloheptene oxides (trans-8 and cis-8) using organolithiums in the presence of(-)-sparteine 16 or (-)-alpha-isosparteine 17 to give predomina ntly 4-silyloxycycloheptanone [(R)-9 (up to 87% ee), a known intermediate i n the synthesis of (S)-physoperuvine (10), and (S)-9 (up to 71% ee), respec tively] is described; the results indicate an alpha-ring opening mechanism. (C) 1999 Elsevier Science Ltd, All rights reserved.