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Lewis acid catalyzed rearrangements of structurally related α,β-unsaturated epoxy ketones and oximes. A complementary approach to the synthesis of isomeric 1,4-diketospiro[n,m] alkanes.

✍ Scribed by Robert D. Bach; Mark W. Tubergen; Russell C. Klix


Publisher
Elsevier Science
Year
1986
Tongue
French
Weight
246 KB
Volume
27
Category
Article
ISSN
0040-4039

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✦ Synopsis


Lew~'s acid catal.vzed rearrangement of cr,B-epoxy o.yimes proceeds b_v oxl'rane cleavage u to the oxime moiety with an attendant pinacol t_vpe alkyd roigration to the resonance stabilized carbenium ion at C, affording a I,_%d2'keto-monoxl'me.

Recent mechanistic studies have provided cogent arguments that carbonyl migrations in u,B-epoxy ketones derived from acyclic enones and their related chlorohydrins are concerted rearrangements that proceed with inversion of configuration at the migration terminus. lp2 Our