Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors.

I. Total Synthesis of Galbulimima Alkaloids. The total synthesis of enantiomerically enriched (+)- and (-)-galbulimima alkaloid 13 is outlined. Sequential use of catalytic cross-coupling and cross-metathesis reactions followed by an intramolecular Diels-Alder reaction provided the required trans-decalin AB ring system and masked the C16-carbonyl as an N-vinyl carbamate for late stage oxidative unveiling as the corresponding C16-enone. Completely diastereoselective introduction of the C-ring via radical cyclization chemistry followed by an enamine-ketone addition for construction of the CDE-ring system allowed rapid entry to the pentacyclic core of these alkaloids. The absolute stereochemistry of natural (-)-galbulimima alkaloid 13 is now unambiguously revised to 2S.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2006

Author dc:creator

• Hunt, Diana Katharine

Advisor dc:contributor.advisor

• Mohammad Movassaghi and Peter H. Seeberger.

• 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/1721.1/38321

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/38321