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Oxidative cyclization reactions of trienes and dienynes: total synthesis of membrarollin

Oxidative cyclization reactions of trienes and dienynes: total synthesis of membrarollin
Oxidative cyclization reactions of trienes and dienynes: total synthesis of membrarollin
Trienes and dienynes containing one electron-deficient double bond were shown to undergo regio- and stereoselective oxidative cyclization in the presence of permanganate ion to afford 2,5-bis hydroxyalkyltetrahydrofurans (THF diols). The THF diols produced retained either alkene or alkyne functionalities, which provided convenient handles for the metal oxo-mediated introduction of an adjacent THF ring with overall control of relative and absolute stereochemistry. Adjacent bis-THFs possessing threo-cis-threo-trans-erythro, threo-cis-threo-trans-threo, threo-cis-threo-cis-erythro, threo-cis-erythro-cis-threo, or threo-cis-erythro-trans-threo relationships were synthesized by appropriate selection of alkene geometry and methodology for the closure of the second ring. The threo-cis-threo-cis-erythro stereochemical arrangement is embodied within the bis-THF core units of a number of Annonaceous acetogenins including membrarollin, while trilobacin has a threo-cis-erythro-trans-threo configured core. As an application of the selective oxidative cyclization approach, a total synthesis of membrarollin was completed in 17 linear steps from dodecyne. The C21,C22 double epimer of membrarollin was also synthesized in 15 linear steps and without recourse to the use of hydroxyl group protection.
0022-3263
981-988
Morris, Claire L.
6db1cb72-7e61-4958-9249-5c6f2f24d6ed
Hu, Yulai
5f6957ca-475f-42b3-892f-e2d64cf2ef11
Head, Geoff D.
72d72d25-0108-4552-9cf2-94755c917c4e
Brown, Lynda J.
75aa95fa-5d27-46a7-9dbe-0f465a664f5b
Whittingham, William G.
f84b39e9-7303-43ad-944e-26d5c8bc3969
Brown, Richard C.D.
21ce697a-7c3a-480e-919f-429a3d8550f5
Morris, Claire L.
6db1cb72-7e61-4958-9249-5c6f2f24d6ed
Hu, Yulai
5f6957ca-475f-42b3-892f-e2d64cf2ef11
Head, Geoff D.
72d72d25-0108-4552-9cf2-94755c917c4e
Brown, Lynda J.
75aa95fa-5d27-46a7-9dbe-0f465a664f5b
Whittingham, William G.
f84b39e9-7303-43ad-944e-26d5c8bc3969
Brown, Richard C.D.
21ce697a-7c3a-480e-919f-429a3d8550f5

Morris, Claire L., Hu, Yulai, Head, Geoff D., Brown, Lynda J., Whittingham, William G. and Brown, Richard C.D. (2009) Oxidative cyclization reactions of trienes and dienynes: total synthesis of membrarollin. Journal of Organic Chemistry, 74 (3), 981-988. (doi:10.1021/Jo802012a). (PMID:19132937)

Record type: Article

Abstract

Trienes and dienynes containing one electron-deficient double bond were shown to undergo regio- and stereoselective oxidative cyclization in the presence of permanganate ion to afford 2,5-bis hydroxyalkyltetrahydrofurans (THF diols). The THF diols produced retained either alkene or alkyne functionalities, which provided convenient handles for the metal oxo-mediated introduction of an adjacent THF ring with overall control of relative and absolute stereochemistry. Adjacent bis-THFs possessing threo-cis-threo-trans-erythro, threo-cis-threo-trans-threo, threo-cis-threo-cis-erythro, threo-cis-erythro-cis-threo, or threo-cis-erythro-trans-threo relationships were synthesized by appropriate selection of alkene geometry and methodology for the closure of the second ring. The threo-cis-threo-cis-erythro stereochemical arrangement is embodied within the bis-THF core units of a number of Annonaceous acetogenins including membrarollin, while trilobacin has a threo-cis-erythro-trans-threo configured core. As an application of the selective oxidative cyclization approach, a total synthesis of membrarollin was completed in 17 linear steps from dodecyne. The C21,C22 double epimer of membrarollin was also synthesized in 15 linear steps and without recourse to the use of hydroxyl group protection.

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Published date: 6 February 2009
Organisations: Chemistry

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Local EPrints ID: 148889
URI: http://eprints.soton.ac.uk/id/eprint/148889
ISSN: 0022-3263
PURE UUID: e39dbdf2-7710-4dcb-b84e-1d1ab569914b
ORCID for Lynda J. Brown: ORCID iD orcid.org/0000-0002-5678-0814
ORCID for Richard C.D. Brown: ORCID iD orcid.org/0000-0003-0156-7087

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Date deposited: 29 Apr 2010 08:56
Last modified: 03 Dec 2019 01:59

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Contributors

Author: Claire L. Morris
Author: Yulai Hu
Author: Geoff D. Head
Author: Lynda J. Brown ORCID iD
Author: William G. Whittingham

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