Enantioselective nucleophile-catalyzed cycloadditions

Chapter 1 describes the development of an asymmetric nucleophile-catalyzed [2+2] cycloaddition of ketenes with aldehydes. This is the first report of a catalytic enantioselective synthesis of trisubstituted [beta]-lactones. Two enantioselective phosphine-catalyzed [3+2] cycloadditions of allenoates are detailed in Chapter 2. A method for the asymmetric synthesis of cyclopentenes via a [3+2] cycloaddition of allenoates with enones is first discussed. This is followed by a report of our efforts to extend this [3+2] methodology to imine electrophiles. We conclude, in Chapter 3, with an account of the development of a novel phosphine-catalyzed synthesis of bicyclo[3.3.0]octanones and bicyclo[4.3.0]nonanones. Preliminary results for an enantioselective variant of this method are also disclosed.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2007

Author dc:creator

• Wilson, Jonathan E., Ph. D. Massachusetts Institute of Technology

Advisor dc:contributor.advisor

• Gregory C. Fu.

• 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/1721.1/40973

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/40973