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Transformations of lignans. Part 11: Oxidation of diphyllin with hypervalent iodine reagents and reductive reactions of a resulting 1-methoxy-1-aryl-4-oxonaphthalene lactone

Transformations of lignans. Part 11: Oxidation of diphyllin with hypervalent iodine reagents and reductive reactions of a resulting 1-methoxy-1-aryl-4-oxonaphthalene lactone
Transformations of lignans. Part 11: Oxidation of diphyllin with hypervalent iodine reagents and reductive reactions of a resulting 1-methoxy-1-aryl-4-oxonaphthalene lactone
Treatment of diphyllin 4 with phenyliodonium diacetate (PIDA) in methanol affords a 1-methoxy-1-aryl-4-oxonaphthalene lactone 6. Reduction of 6 with lithium aluminium hydride yields, inter alia, 3,4-dihydrodiphyllin 13, while reaction with sodium in ethanol yields 8 as a major product. These reactions illustrate that selective oxidation followed by reduction provides a facile route for the conversion of a 1-arylnaphthalene lactone to novel functionalised naphthalene and dihydronaphthalene derivatives. Of particular interest is that the oxidation indirectly activates the methylene position (C-10) of the ?-lactone, which may then potentially be substituted to give a new series of lignans. Reaction of 6 with hydroxylamine and benzyloxyamine also proceeds by way of initial attack at C-10.
lignans, oxidative nucleophilic substitutions, diphyllin, synthesis, 3, 4-dihydrodiphyllin, oxazinone, benzyloxyoxime acid-catalyzed rearrangements, 2, 6-diaryl-3, 7-dioxabicyclooctane skeleton, phenolic dibenzylbutyrolactones, biomimetic synthesis, bf3-etherate, gmelinol, ddq, triethylsilane, derivatives, product
0040-4020
4463-4473
Venkateswarlu, R.
0c39e41d-3313-4e8e-9695-414352077da5
Kamakshi, C.
9765f480-fcb2-407b-8929-bec5722fb6ed
Subhash, P.V.
c24704a8-5b2f-4969-911c-21a7b19e0059
Moinuddin, S.G.A.
6c75de51-2d86-443c-8d9d-baa3531dc2cc
Reddy, D. Rama Sekhara
ef68c817-87c3-4b6f-be74-f4c6f32ca5b6
Ward, R.S.
f65b520a-c9fc-46af-b033-ce6dbc95a8a5
Pelter, A.
d73e99e4-3dad-452c-aee3-3f9818832d9a
Gelbrich, T.
42309d69-eaf1-4bb7-ba2e-db61f338e370
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Light, M.E.
cf57314e-6856-491b-a8d2-2dffc452e161
Venkateswarlu, R.
0c39e41d-3313-4e8e-9695-414352077da5
Kamakshi, C.
9765f480-fcb2-407b-8929-bec5722fb6ed
Subhash, P.V.
c24704a8-5b2f-4969-911c-21a7b19e0059
Moinuddin, S.G.A.
6c75de51-2d86-443c-8d9d-baa3531dc2cc
Reddy, D. Rama Sekhara
ef68c817-87c3-4b6f-be74-f4c6f32ca5b6
Ward, R.S.
f65b520a-c9fc-46af-b033-ce6dbc95a8a5
Pelter, A.
d73e99e4-3dad-452c-aee3-3f9818832d9a
Gelbrich, T.
42309d69-eaf1-4bb7-ba2e-db61f338e370
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Light, M.E.
cf57314e-6856-491b-a8d2-2dffc452e161

Venkateswarlu, R., Kamakshi, C., Subhash, P.V., Moinuddin, S.G.A., Reddy, D. Rama Sekhara, Ward, R.S., Pelter, A., Gelbrich, T., Hursthouse, M.B., Coles, S.J. and Light, M.E. (2006) Transformations of lignans. Part 11: Oxidation of diphyllin with hypervalent iodine reagents and reductive reactions of a resulting 1-methoxy-1-aryl-4-oxonaphthalene lactone. Tetrahedron, 62 (18), 4463-4473. (doi:10.1016/j.tet.2006.02.050).

Record type: Article

Abstract

Treatment of diphyllin 4 with phenyliodonium diacetate (PIDA) in methanol affords a 1-methoxy-1-aryl-4-oxonaphthalene lactone 6. Reduction of 6 with lithium aluminium hydride yields, inter alia, 3,4-dihydrodiphyllin 13, while reaction with sodium in ethanol yields 8 as a major product. These reactions illustrate that selective oxidation followed by reduction provides a facile route for the conversion of a 1-arylnaphthalene lactone to novel functionalised naphthalene and dihydronaphthalene derivatives. Of particular interest is that the oxidation indirectly activates the methylene position (C-10) of the ?-lactone, which may then potentially be substituted to give a new series of lignans. Reaction of 6 with hydroxylamine and benzyloxyamine also proceeds by way of initial attack at C-10.

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More information

Published date: 2006
Keywords: lignans, oxidative nucleophilic substitutions, diphyllin, synthesis, 3, 4-dihydrodiphyllin, oxazinone, benzyloxyoxime acid-catalyzed rearrangements, 2, 6-diaryl-3, 7-dioxabicyclooctane skeleton, phenolic dibenzylbutyrolactones, biomimetic synthesis, bf3-etherate, gmelinol, ddq, triethylsilane, derivatives, product

Identifiers

Local EPrints ID: 44562
URI: http://eprints.soton.ac.uk/id/eprint/44562
ISSN: 0040-4020
PURE UUID: 27444ba9-b552-468d-88a2-62759529eb97
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for M.E. Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 28 Feb 2007
Last modified: 16 Mar 2024 03:05

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Contributors

Author: R. Venkateswarlu
Author: C. Kamakshi
Author: P.V. Subhash
Author: S.G.A. Moinuddin
Author: D. Rama Sekhara Reddy
Author: R.S. Ward
Author: A. Pelter
Author: T. Gelbrich
Author: M.B. Hursthouse
Author: S.J. Coles ORCID iD
Author: M.E. Light ORCID iD

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