Taxane synthesis via (2+2) photoaddition fragmentation chemistry with a novel beta-ketoester equivalent.

Format:

Book

Thesis/Dissertation

Author/Creator:

Havran, Lisa Marie.

Contributor:

University of Pennsylvania.

Language:

English

Subjects (All):

Chemistry, Organic.

0490.

Local Subjects:

0490.

Physical Description:

426 pages

Contained In:

Dissertation Abstracts International 58-11B.

System Details:

Mode of access: World Wide Web.

text file

Summary:

This dissertation describes the preparation of the tricyclic skeleton 3.64 of taxol (1.1) from readily available Wieland-Miescher ketone 2.42. This route features the use of a newly developed $\beta$-ketoester equivalent, oxazinone heterocycle 3.60, as a substrate for (2+2) photoaddition fragmentation chemistry.*

In the taxane systems described, it was found that the oxazinone heterocycle can be formed in higher yields and under milder conditions than the previously employed dioxenone. Conditions for oxazinone formation and fragmentation were tested and optimized on several simple models systems, and were then applied to the synthesis of taxanes.*

Due to the milder conditions required for oxazinone formation, efforts were undertaken to further functionalize the photosubstrate prior to tricycle formation. To this end, the preparation of compound 3.147, which contains the oxetane D ring as well as the C-2 and C-4 oxygenation of taxol, is described. Further elaboration of this compound to the oxazinone photosubstrate is currently under investigation.* ftn*Please refer to the dissertation for diagrams.

Notes:

Source: Dissertation Abstracts International, Volume: 58-11, Section: B, page: 5966.

Supervisor: Jeffrey D. Winkler.

Thesis (Ph.D.)--University of Pennsylvania, 1997.

Local Notes:

School code: 0175.

ISBN:

9780591659474

Access Restriction:

Restricted for use by site license.