An approach to the synthesis of gelsemine: the intramolecular reaction of an allylsilane with an acyliminium ion for the synthesis of one of the quaternary centres 1 1 No reprints available.

Carol Clarke; Ian Fleming; Joseph M.D. Fortunak; Peter T. Gallagher; Matthew C. Honan; André Mann; Christoph O. Nübling; Paul R. Raithby; J. Jens Wolff

doi:10.1016/S0040-4020(01)86646-1

An approach to the synthesis of gelsemine: the intramolecular reaction of an allylsilane with an acyliminium ion for the synthesis of one of the quaternary centres ¹ 1 No reprints available.

Carol Clarke, Ian Fleming, Joseph M.D. Fortunak, Peter T. Gallagher, Matthew C. Honan, André Mann, Christoph O. Nübling, Paul R. Raithby, J. Jens Wolff

University of Cambridge

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

Abstract

We describe an efficient synthesis (summarised in Schemes 8 and 10) of an advanced intermediate (34) suitable for the synthesis of gelsemine. The key steps in the synthesis are (i) the Diels-Alder reaction between 1-tetrahydropyranyloxycyclohexa-1,3-diene (10) and methyl β-nitroacrylate (11) giving an adduct (12), in which the chiral centre in the tetrahydropyranyl ring is produced substantially in only one sense, (ii) the rearrangement of a bicyclo [2.2.2] octane (23) into a bicyclo[ 3.2.1] octane (24), where control of which bridge migrates is achieved by a choice of the counterion in the Lewis acid, and (iii) the efficient formation of the quaternary centre by an intramolecular reaction between an allylsilane group and an acyliminium ion (33 → 34).

Original language	English
Pages (from-to)	3931-3944
Number of pages	14
Journal	Tetrahedron
Volume	44
Issue number	13
DOIs	https://doi.org/10.1016/S0040-4020(01)86646-1
Publication status	Published - 31 Dec 1988

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/S0040-4020(01)86646-1

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Clarke, C., Fleming, I., Fortunak, J. M. D., Gallagher, P. T., Honan, M. C., Mann, A., Nübling, C. O., Raithby, P. R., & Wolff, J. J. (1988). An approach to the synthesis of gelsemine: the intramolecular reaction of an allylsilane with an acyliminium ion for the synthesis of one of the quaternary centres ¹ 1 No reprints available. Tetrahedron, 44(13), 3931-3944. https://doi.org/10.1016/S0040-4020(01)86646-1

An approach to the synthesis of gelsemine: the intramolecular reaction of an allylsilane with an acyliminium ion for the synthesis of one of the quaternary centres ¹ 1 No reprints available. / Clarke, Carol; Fleming, Ian; Fortunak, Joseph M.D. et al.
In: Tetrahedron, Vol. 44, No. 13, 31.12.1988, p. 3931-3944.

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

Clarke, C, Fleming, I, Fortunak, JMD, Gallagher, PT, Honan, MC, Mann, A, Nübling, CO, Raithby, PR & Wolff, JJ 1988, 'An approach to the synthesis of gelsemine: the intramolecular reaction of an allylsilane with an acyliminium ion for the synthesis of one of the quaternary centres ¹ 1 No reprints available.', Tetrahedron, vol. 44, no. 13, pp. 3931-3944. https://doi.org/10.1016/S0040-4020(01)86646-1

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title = "An approach to the synthesis of gelsemine: the intramolecular reaction of an allylsilane with an acyliminium ion for the synthesis of one of the quaternary centres 1 1 No reprints available.",

abstract = "We describe an efficient synthesis (summarised in Schemes 8 and 10) of an advanced intermediate (34) suitable for the synthesis of gelsemine. The key steps in the synthesis are (i) the Diels-Alder reaction between 1-tetrahydropyranyloxycyclohexa-1,3-diene (10) and methyl β-nitroacrylate (11) giving an adduct (12), in which the chiral centre in the tetrahydropyranyl ring is produced substantially in only one sense, (ii) the rearrangement of a bicyclo [2.2.2] octane (23) into a bicyclo[ 3.2.1] octane (24), where control of which bridge migrates is achieved by a choice of the counterion in the Lewis acid, and (iii) the efficient formation of the quaternary centre by an intramolecular reaction between an allylsilane group and an acyliminium ion (33 → 34).",

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AB - We describe an efficient synthesis (summarised in Schemes 8 and 10) of an advanced intermediate (34) suitable for the synthesis of gelsemine. The key steps in the synthesis are (i) the Diels-Alder reaction between 1-tetrahydropyranyloxycyclohexa-1,3-diene (10) and methyl β-nitroacrylate (11) giving an adduct (12), in which the chiral centre in the tetrahydropyranyl ring is produced substantially in only one sense, (ii) the rearrangement of a bicyclo [2.2.2] octane (23) into a bicyclo[ 3.2.1] octane (24), where control of which bridge migrates is achieved by a choice of the counterion in the Lewis acid, and (iii) the efficient formation of the quaternary centre by an intramolecular reaction between an allylsilane group and an acyliminium ion (33 → 34).

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An approach to the synthesis of gelsemine: the intramolecular reaction of an allylsilane with an acyliminium ion for the synthesis of one of the quaternary centres ¹ 1 No reprints available.

Abstract

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