- General Synthetic Approach to Rotenoids via Stereospecific, Group-Selective 1,2-Rearrangement and Dual S N Ar Cyclizations of Aryl Fluorides
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A general synthetic approach to rotenoids is described, featuring 1) stereospecific, group-selective 1,2-rearrangements of epoxy alcohols, and 2) S N Ar oxy-cyclizations of aryl fluorides. The common intermediate epoxyketone, en route to (-)-rotenone and (-)-deguelin, was prepared from d -araboascorbic acid in five steps. Also described is the conversion of (-)-deguelin into oxidized congeners, (-)-tephrosin and (+)-12a- epi -tephrosin.
- Matsuoka, Seiya,Nakamura, Kayo,Ohmori, Ken,Suzuki, Keisuke
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p. 1139 - 1156
(2019/02/26)
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- Stereocontrolled Total Syntheses of (?)-Rotenone and (?)-Dalpanol by 1,2-Rearrangement and SNAr Oxycyclizations
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The total syntheses of (?)-rotenone and (?)-dalpanol have been achieved by a group-selective, stereospecific 1,2-shift of an epoxy alcohol and SNAr cyclizations. Three oxacycles are constructed, thus illustrating a versatile synthetic route to various rotenoids.
- Nakamura, Kayo,Ohmori, Ken,Suzuki, Keisuke
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supporting information
p. 182 - 187
(2016/12/30)
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- Synthesis of trans-B/C-Rotenoids: X-Ray and NMR Data for cis- and trans-Forms of Isorotenone
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Reduction of 6a,12a-didehydrorotenoids with diisobutylaluminium hydride gives clean 1,4-reduction leading to unstable trans-B/C-fusions, not previously known for enolisable rotenoids: they are epimerised to stable cis-forms under acid conditions.Applied initially to isorotenone, the method is extended to trans-B/C-deguelin, α-toxicarol, the 'core' rotenoid structure and the 6aS,12aR,5'R- and 6aR,12aS,5'R-rotenone stereoisomers. 1H and 13C NMR data are compared for the cis- and trans-forms and the geometry and conformations of the isorotenones are compared by X-ray analysis, providing insight into the reasons for the instability of the trans-forms.Reduction of the ridge-tile-like cis-isorotenone by sodium borohydride occurs from one face to give a cis-12α-hydroxy product, whilst the flatter trans-structure is attacked from both faces to give trans-12α- and 12β-hydroxy products.
- Begley, Michael J.,Crombie, Leslie,Hadi, Hamid bin A.,Josephs, Jonathan L.
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p. 2605 - 2614
(2007/10/02)
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- Aryloxymethyl Radical Cyclizations Mimicking Biological C-C Bond Formation to Methoxy Groups
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Attention is drawn to a small group of diverse natural products whose biosynthesis is unusual in involving formation of O-heterocyclic rings by C-C bond formation to aromatic methoxy groups, in net oxidative and non-oxidative processes.It is shown that ar
- Ahmad-Junan, S. Asiah,Walkington, Andrew J.,Whiting, Donald A.
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p. 2313 - 2320
(2007/10/02)
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- Synthesis of Novel Labile Rotenoids with Unnatural trans-B/C Ring Systems
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6a,12a-Dehydrorotenoids are cleanly reduced in 1,4-fashion by DIBAL to give rotenoids having the unstable, unnatural, trans-B/C fusion, readily epimerised by acid to the cis-forms: an X-ray structure for (+/-)-trans-isorotenone confirms the nature of the ring fusion.
- Begley, Michael J.,Crombie, Leslie,Hadi, A. Hamid bin A.,Josephs, Jonathan L.
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p. 204 - 205
(2007/10/02)
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- New Synthetic Methods in Rotenoid Chemistry: - and -(-)-Rotenone and (+/-)-Isorotenone
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A reconstructive circuit for 13C- and 14C-labelling of the 7'-methylene group of (-)-rotenone is described.It involves blocking the enolisable 12a-site with a trimethylsilyloxy-group, followed by removal and reintroduction of the methylene, and elision of
- Carson, David,Cass, Malcolm W.,Crombie, Leslie,Holden, Ian,Whiting, Donald A.
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p. 773 - 778
(2007/10/02)
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