Bromonium-Initiated Epoxide-Opening Cascades : total Synthesis of ent-Dioxepandehydrothyrsiferol and Synthetic Studies toward (+)-Scholarisine A

CHAPTER I. Bromonium-Initiated Epoxide-Opening Cascades: Total Synthesis of ent-Dioxepandehydrothyrsiferol Our foray into the total synthesis of ent-dioxepandehydrothyrsiferol has led to the discovery and development of the bromonium-initiated epoxide-opening cascade. This transformation constructs the signature trans-anti-trans tricyclic portion of the natural product containing the bromo-oxepane in a single step. Further explorations into this cascade also revealed feasibility of incorporation of exogenous trapping nucleophiles into the reaction. [chemical formulae] CHAPTER 11. Synthetic Studies toward (+)-Scholarisine A. A concise and scalable route toward the monoterpene indole alkaloid (+)- scholarisine A has been developed. Synthetic highlights of the route include: 1) cisselective Diels-Alder cycloaddition reaction to construct strained 5,6-fused hydrindanones, 2) a novel indole formation via an in-situ aza-Wittig reaction, and 3) a selective enolization and hydrolysis sequence of a diketone substrate to provide rapid access to a key tetracyclic intermediate. Studies to access the natural product via latestage intramolecular indole alkylations are presented. [chemical formulae]

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2013

Author dc:creator

• Tanuwidjaja, Jessica

Advisor dc:contributor.advisor

• Timothy F. Jamison.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/79260

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/79260