Peer-Reviewed Journal Details
Mandatory Fields
Burnell, ES;Irshad, AR;Lee, ATL;Thomas, EJ
2018
November
Tetrahedron
Synthetic approaches to phomactins: Late stage stereochemical and reactivity issues
Published
()
Optional Fields
REDUCTIVE LITHIATION PHENYLSULFONES REARRANGEMENTS CYCLIZATION ANTAGONISTS PRECURSORS CLEAVAGE
74
6737
6748
Oxidation of a 15-methylenebicyclo[9.3.1]pentadeca-3,7-dien-14-ol with a 10-phenylsulfonyl substituent provided a 14-oxobicyclo[9.3.1]pentadeca-1(15),3,7-triene-15-carbaldehyde that on reduction with DIBAL-H was converted into a 15-hydroxymethylbicyclo[9.3.1 ]pentadeca-1(15),3,7-triene-14-ol with the relative configuration at C14 required for incorporation into a synthesis of phomactin A. The oxidation and reduction of an analogous 3,4-epoxide that lacked the 10-phenylsulfonyl group gave a diol with the opposite relative configuration at C14. However, the TPAP oxidation and DIBAL-H reduction of a 14-hydroxy-15-methylene-3,4-epoxide that still had the 10-phenylsulfonyl group gave a diol with the required configuration at C14 although the expected spontaneous participation of the 14-hydroxyl group in an intramolecular epoxide ring-opening was only observed under Lewis acidic conditions. (C) 2018 Elsevier Ltd. All rights reserved.
0040-4020
10.1016/j.tet.2018.10.004
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