Nickel-catalyzed Suzuki-Miyaura reactions of unactivated halides with alkyl boranes and planar-chiral borabenzene catalysts for Diels-Alder reactions

Part I describes the expansion in scope of a nickel-catalyzed coupling reaction of unactivated alkyl bromides and alkyl boranes to include unactivated alkyl chlorides. The new method is adapted for use outside of a glove box and is also found to be applicable not only to the coupling of primary chlorides, but also to the coupling of bromides and iodides, both primary and secondary. ... This coupling reaction of chlorides is further adapted to the of p-chloro aryl alkyl amines. This work constitutes an extension directing groups for the asymmetric Suzuki-Miyaura reactions halides. ... Part II details work towards an asymmetric Diels-Alder reaction between cyclopentadiene and methacrolein catalyzed by a planar-chiral boron Lewis acid. This system exhibits a level of turnover that is unprecedented in reactions mediated by planar chiral boron heterocycles. Computational studies shed light on the nature of the 7tsymmetry interaction between borabenzenes and complexed carbonyl groups. The selectivity of the borabenzene-catalyzed Diels-Alder reaction is also examined.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2010

Author dc:creator

• Lu, Zhe

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/1721.1/62101

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/62101