The acid-catalyzed oxido-reduction of spiroketals. Evidence for stereoelectronic control in hydride transfer to cyclic oxenium ions
Keyword(s):
Tricyclic spiroketal 1 undergoes an acid-catalyzed oxidation–reduction reaction which yields equatorial bicyclic ether aldehyde 5 specifically. Similarly, spiroketals 2, 3, and 4 give equatorial bicyclic ether ketone 12. These results are interpreted by invoking an internal hydride transfer from an alcohol function to a cyclic oxenium ion which takes place with stereoelectronic control. The reduction of tricyclic ketals 1 and 22 with sodium cyanoborohydride under acidic conditions is also reported.
1974 ◽
Vol 39
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pp. 3024-3029
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2009 ◽
Vol 2
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pp. 59-63
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1979 ◽
Vol 105
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pp. 71-83
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Keyword(s):
1996 ◽
Vol 79
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pp. 491-494
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2014 ◽
Vol 6
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pp. 4254-4263
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