HIGHLY FUNCTIONALIZED CYCLOHEXENYL SYSTEMS - ENZYMATIC RESOLUTION ANDSELECTIVE OXIRANE OPENING REACTIONS OF P-BENZOQUINONE DERIVATIVES

Citation
Jt. Kohrt et al., HIGHLY FUNCTIONALIZED CYCLOHEXENYL SYSTEMS - ENZYMATIC RESOLUTION ANDSELECTIVE OXIRANE OPENING REACTIONS OF P-BENZOQUINONE DERIVATIVES, Journal of organic chemistry, 63(15), 1998, pp. 5088-5093
Citations number
45
Categorie Soggetti
Chemistry Inorganic & Nuclear
ISSN journal
00223263
Volume
63
Issue
15
Year of publication
1998
Pages
5088 - 5093
Database
ISI
SICI code
0022-3263(1998)63:15<5088:HFCS-E>2.0.ZU;2-C
Abstract
Diol 2, derived in two steps from p-benzoquinone, was converted to epo xy alcohol 3. The latter was resolved with crude Candida rugosa lipase in isopropenyl acetate/toluene to give acetate (-)-4 and residual alc ohol (+)-3. Oxirane ring opening reactions of 3 and the corresponding acetate and TBDMS derivatives with a variety of nucleophiles gave dias tereomerically pure 3,4,5,6-tetrasubstituted cyclohexene derivatives o f type 6. X-ray crystal structures were obtained on compounds 6e, 6m a nd the diacetate prepared from 6l. Nitrogen nucleophiles provided entr y in various aziridines 10. Pd(0)-catalyzed nucleophilic additions to substrate 5 cleanly provided the diastereomeric pattern of type 11. tr ans-5,6-Disubstituted cyclohexadienes 13 were obtained by an unusual s yn-reductive elimination on bromocarbonates 12 utilizing Pd or Zn.