Lewis acid catalysed rearrangements of unsaturated bicyclic [2.2.n] endoperoxides in the presence of vinyl silanes; access to novel Fenozan BO-7 analogues

Paul M. O'Neill; Sarah L. Rawe; Richard C. Storr; Steve Ward; Gary H. Posner

doi:10.1016/j.tetlet.2005.03.022

Lewis acid catalysed rearrangements of unsaturated bicyclic [2.2.n] endoperoxides in the presence of vinyl silanes; access to novel Fenozan BO-7 analogues

Paul M. O'Neill, Sarah L. Rawe, Richard C. Storr, Steve Ward, Gary H. Posner

Tropical Disease Biology

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

12 Citations (Scopus)

Abstract

Reactions of a series of unsaturated bicyclic [2.2.n] endoperoxides with allyltrimethylsilane in the presence TMSOTf or SnCl4 provides the cis-configured endoperoxides 9a-12. It is proposed that this novel reaction proceeds via attack of the allylsilane on the carbocation derived from heterolytic cleavage of the endoperoxide bridge. The reaction proceeds with a high degree of diastereoselectivity and we propose that the bulky -CH2SiMe3 substituent adopts an equatorial position in a product-like transition state. In contrast to Fenozan B0-7, these compounds displayed poor antimalarial activity versus chloroquine-resistant parasites in vitro. (c) 2005 Published by Elsevier Ltd.

Original language	English
Pages (from-to)	3029-3032
Number of pages	4
Journal	Tetrahedron Letters
Volume	46
Issue number	17
DOIs	https://doi.org/10.1016/j.tetlet.2005.03.022
Publication status	Published - 25 Apr 2005

Keywords

Antimalarial
Artemisinin
Endoperoxide

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10.1016/j.tetlet.2005.03.022

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title = "Lewis acid catalysed rearrangements of unsaturated bicyclic [2.2.n] endoperoxides in the presence of vinyl silanes; access to novel Fenozan BO-7 analogues",

abstract = "Reactions of a series of unsaturated bicyclic [2.2.n] endoperoxides with allyltrimethylsilane in the presence TMSOTf or SnCl4 provides the cis-configured endoperoxides 9a-12. It is proposed that this novel reaction proceeds via attack of the allylsilane on the carbocation derived from heterolytic cleavage of the endoperoxide bridge. The reaction proceeds with a high degree of diastereoselectivity and we propose that the bulky -CH2SiMe3 substituent adopts an equatorial position in a product-like transition state. In contrast to Fenozan B0-7, these compounds displayed poor antimalarial activity versus chloroquine-resistant parasites in vitro. (c) 2005 Published by Elsevier Ltd.",

keywords = "Antimalarial, Artemisinin, Endoperoxide",

author = "O'Neill, \{Paul M.\} and Rawe, \{Sarah L.\} and Storr, \{Richard C.\} and Steve Ward and Posner, \{Gary H.\}",

year = "2005",

month = apr,

day = "25",

doi = "10.1016/j.tetlet.2005.03.022",

language = "English",

volume = "46",

pages = "3029--3032",

journal = "Tetrahedron Letters",

issn = "0040-4039",

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number = "17",

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TY - JOUR

T1 - Lewis acid catalysed rearrangements of unsaturated bicyclic [2.2.n] endoperoxides in the presence of vinyl silanes; access to novel Fenozan BO-7 analogues

AU - O'Neill, Paul M.

AU - Rawe, Sarah L.

AU - Storr, Richard C.

AU - Ward, Steve

AU - Posner, Gary H.

PY - 2005/4/25

Y1 - 2005/4/25

N2 - Reactions of a series of unsaturated bicyclic [2.2.n] endoperoxides with allyltrimethylsilane in the presence TMSOTf or SnCl4 provides the cis-configured endoperoxides 9a-12. It is proposed that this novel reaction proceeds via attack of the allylsilane on the carbocation derived from heterolytic cleavage of the endoperoxide bridge. The reaction proceeds with a high degree of diastereoselectivity and we propose that the bulky -CH2SiMe3 substituent adopts an equatorial position in a product-like transition state. In contrast to Fenozan B0-7, these compounds displayed poor antimalarial activity versus chloroquine-resistant parasites in vitro. (c) 2005 Published by Elsevier Ltd.

AB - Reactions of a series of unsaturated bicyclic [2.2.n] endoperoxides with allyltrimethylsilane in the presence TMSOTf or SnCl4 provides the cis-configured endoperoxides 9a-12. It is proposed that this novel reaction proceeds via attack of the allylsilane on the carbocation derived from heterolytic cleavage of the endoperoxide bridge. The reaction proceeds with a high degree of diastereoselectivity and we propose that the bulky -CH2SiMe3 substituent adopts an equatorial position in a product-like transition state. In contrast to Fenozan B0-7, these compounds displayed poor antimalarial activity versus chloroquine-resistant parasites in vitro. (c) 2005 Published by Elsevier Ltd.

KW - Antimalarial

KW - Artemisinin

KW - Endoperoxide

U2 - 10.1016/j.tetlet.2005.03.022

DO - 10.1016/j.tetlet.2005.03.022

M3 - Article

SN - 0040-4039

VL - 46

SP - 3029

EP - 3032

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 17

ER -

Lewis acid catalysed rearrangements of unsaturated bicyclic [2.2.n] endoperoxides in the presence of vinyl silanes; access to novel Fenozan BO-7 analogues

Abstract

Keywords

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