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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Stereocontrolled syntheses of carbocyclic C-nucleosides and related compounds
1Department of Pharmaceutical and Biomedical Sciences, College of Pharmacy, The University of Georgia, Athens, Georgia 30602, USA.
Abstract:
Carbocyclic 9-deazapurine nucleosides (1-4), a spiranic pyrimidone carbocyclic compound (5), and an unusual carbocyclic isonucleoside (6) were prepared as enantiomerically pure compounds via the key intermediates 10 and 21 from 1,4-gamma-ribonolactone. The key intermediate 10 was prepared by stereoselective reduction with Bu3SnH and then converted to carbocyclic C-ribonucleosides 1, 3, and 4. 2',3'-Didehydro-2',3'-dideoxycarbocyclic 9-deazainosine (2) was prepared from a 2',3'-dimesylate 17 by treatment with Li2Te followed by an acidic deprotection. The key bicyclic intermediate 21 was prepared from a diol 20 by an intramolecular cyclization using CHI3-Ph3P-imidazole and converted to the spiranic compound 5 and an olefinic nucleoside 6 by the construction of the heterocyclic moiety followed by deprotection.
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