|
|||||
|
|
Lewis acid catalysed rearrangements of unsaturated bicyclic [2.2.n] endoperoxides in the presence of vinyl silanes; access to novel Fenozan BO-7 analogues |
|
| Authors: | Paul M. O&rsquo Neill,Sarah L. Rawe,Stephen A. Ward |
| Affiliation: | a Department of Chemistry, The Robert Robinson Laboratories, University of Liverpool, Liverpool L69 7ZD, UK b Liverpool School of Tropical Medicine, University of Liverpool, Pembroke Place, Liverpool L3 5QA, UK c Department of Chemistry, School of Arts and Sciences, The Johns Hopkins University, Baltimore, MD 21218, USA |
| 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. |
| Keywords: | Artemisinin Endoperoxide Antimalarial |
| 本文献已被 ScienceDirect 等数据库收录！ | |