Progress in nucleophilic catalysis and development of nickel-catalyzed cross-couplings of propargylic halides

Chapter 1 describes the development of two organocatalytic processes. The first is a 13-alkylation reaction of Michael acceptors, and represents a novel umpolung process catalyzed by N-heterocyclic carbenes. The second section discusses the first successful phosphine-catalyzed, y-alkylation reaction of isomerizable allenoates. A highly enantioselective variant of this reaction is described. Chapter 2 discusses nickel-catalyzed cross-coupling reactions of secondary propargylic halides with a variety of organozinc nucleophiles. Section 2.2 describes progress toward an asymmetric alkylation reaction. In Section 2.3, the development of the first alkyl-alkyl secondary-secondary cross-coupling is described; Section 2.4 describes the application of this coupling reaction to the formal synthesis of a-cembra-2,7,1 1-triene-4,6-diol. The last section of this thesis (Section 2.5) discusses the development of the first asymmetric Negishi reaction of arylzinc reagents with secondary electrophiles.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2009

Author dc:creator

• Smith, Sean W. (Sean Wesley)

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/1721.1/49745

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/49745