Exploitation of chemical predisposition in synthesis: An approach to the manzamenones

Saleh Al-Busafi; Jeremy R. Doncaster; Michael G B Drew; Andrew C. Regana; Roger C. Whitehead

doi:10.1039/b110829h

Exploitation of chemical predisposition in synthesis: An approach to the manzamenones

Saleh Al-Busafi, Jeremy R. Doncaster, Michael G B Drew, Andrew C. Regana, Roger C. Whitehead

Research output: Contribution to journal › Article › peer-review

Abstract

Full details of the syntheses of manzamenones A, C and F are reported, using an approach modelled on a plausible biogenetic theory. The key step of the approach is a "one-pot" conversion of the antileukemic cyclopentenone, untenone A, to manzamenone A which occurs in reasonable yield and which proceedsvia a reaction sequence of dehydration, Diels-Alder dimerisation and retro-Dieckmann reaction. The synthetic approach has also been applied to the preparation of a number of shorter alkyl chain analogues of the natural products. Using a combination of NMR and X-ray crystallographic data for the shorter alkyl chain analogues of manzamenone A, it is suggested that the relative stereostructures of the majority of the manzamenones should be revised such that the acyl group at the C2 position lies on α-face and that at the C5 position resides on the β-face.

Original language	English
Pages (from-to)	476-484
Number of pages	8
Journal	Journal of the Chemical Society. Perkin Transactions 1
Issue number	4
DOIs	https://doi.org/10.1039/b110829h
Publication status	Published - 2002

Keywords

Diels-Alder reaction (dimerization; exploitation of chem. predisposition in a synthetic approach to the manzamenones); Dehydration reaction; Stereoselective synthesis (exploitation of chem. predisposition in a synthetic approach to the manzamenones); Conformation (mol. modeling; of manzamenone analogs); Crystal structure (relative stereostructure from; of manzamenone analogs); Dieckmann condensation (retro-; exploitation of chem. predisposition in a synthetic approach to the manzamenones); Molecular structure (revision, relative stereostructure; of manzamenones); Natural products Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (tetrahydroindenone; exploitation of chem. predisposition in a synthetic approach to the manzamenones)

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10.1039/b110829h

CCDC 158875: Experimental Crystal Structure Determination
Al-Busafi, S. (Contributor), Doncaster, J. (Contributor), Drew, M. G. B. (Contributor), Regan, A. (Contributor) & Whitehead, R. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2002
DOI: 10.5517/cc5bb0t, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc5bb0t&sid=DataCite
Dataset
CCDC 175318: Experimental Crystal Structure Determination
Al-Busafi, S. (Contributor), Drew, M. G. B. (Contributor), Sanders, T. (Contributor) & Whitehead, R. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 1999
DOI: 10.5517/cc5wffw, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc5wffw&sid=DataCite
Dataset

Cite this

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title = "Exploitation of chemical predisposition in synthesis: An approach to the manzamenones",

abstract = "Full details of the syntheses of manzamenones A, C and F are reported, using an approach modelled on a plausible biogenetic theory. The key step of the approach is a {"}one-pot{"} conversion of the antileukemic cyclopentenone, untenone A, to manzamenone A which occurs in reasonable yield and which proceedsvia a reaction sequence of dehydration, Diels-Alder dimerisation and retro-Dieckmann reaction. The synthetic approach has also been applied to the preparation of a number of shorter alkyl chain analogues of the natural products. Using a combination of NMR and X-ray crystallographic data for the shorter alkyl chain analogues of manzamenone A, it is suggested that the relative stereostructures of the majority of the manzamenones should be revised such that the acyl group at the C2 position lies on α-face and that at the C5 position resides on the β-face.",

keywords = "Diels-Alder reaction (dimerization; exploitation of chem. predisposition in a synthetic approach to the manzamenones); Dehydration reaction; Stereoselective synthesis (exploitation of chem. predisposition in a synthetic approach to the manzamenones); Conformation (mol. modeling; of manzamenone analogs); Crystal structure (relative stereostructure from; of manzamenone analogs); Dieckmann condensation (retro-; exploitation of chem. predisposition in a synthetic approach to the manzamenones); Molecular structure (revision, relative stereostructure; of manzamenones); Natural products Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (tetrahydroindenone; exploitation of chem. predisposition in a synthetic approach to the manzamenones)",

author = "Saleh Al-Busafi and Doncaster, {Jeremy R.} and Drew, {Michael G B} and Regana, {Andrew C.} and Whitehead, {Roger C.}",

year = "2002",

doi = "10.1039/b110829h",

language = "English",

pages = "476--484",

journal = "Journal of the Chemical Society. Perkin Transactions 1",

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AU - Al-Busafi, Saleh

AU - Doncaster, Jeremy R.

AU - Drew, Michael G B

AU - Regana, Andrew C.

AU - Whitehead, Roger C.

PY - 2002

Y1 - 2002

N2 - Full details of the syntheses of manzamenones A, C and F are reported, using an approach modelled on a plausible biogenetic theory. The key step of the approach is a "one-pot" conversion of the antileukemic cyclopentenone, untenone A, to manzamenone A which occurs in reasonable yield and which proceedsvia a reaction sequence of dehydration, Diels-Alder dimerisation and retro-Dieckmann reaction. The synthetic approach has also been applied to the preparation of a number of shorter alkyl chain analogues of the natural products. Using a combination of NMR and X-ray crystallographic data for the shorter alkyl chain analogues of manzamenone A, it is suggested that the relative stereostructures of the majority of the manzamenones should be revised such that the acyl group at the C2 position lies on α-face and that at the C5 position resides on the β-face.

AB - Full details of the syntheses of manzamenones A, C and F are reported, using an approach modelled on a plausible biogenetic theory. The key step of the approach is a "one-pot" conversion of the antileukemic cyclopentenone, untenone A, to manzamenone A which occurs in reasonable yield and which proceedsvia a reaction sequence of dehydration, Diels-Alder dimerisation and retro-Dieckmann reaction. The synthetic approach has also been applied to the preparation of a number of shorter alkyl chain analogues of the natural products. Using a combination of NMR and X-ray crystallographic data for the shorter alkyl chain analogues of manzamenone A, it is suggested that the relative stereostructures of the majority of the manzamenones should be revised such that the acyl group at the C2 position lies on α-face and that at the C5 position resides on the β-face.

KW - Diels-Alder reaction (dimerization; exploitation of chem. predisposition in a synthetic approach to the manzamenones); Dehydration reaction; Stereoselective synthesis (exploitation of chem. predisposition in a synthetic approach to the manzamenones); Conf

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DO - 10.1039/b110829h

M3 - Article

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SP - 476

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JO - Journal of the Chemical Society. Perkin Transactions 1

JF - Journal of the Chemical Society. Perkin Transactions 1

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Exploitation of chemical predisposition in synthesis: An approach to the manzamenones

Abstract

Keywords

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Datasets

CCDC 158875: Experimental Crystal Structure Determination

CCDC 175318: Experimental Crystal Structure Determination

Cite this