Stereochemical Course of the Tandem [4+2]/[3+2] Cycloaddition of Nitroalkenes

The [4+2] cycloaddition of nitrobutene was further examined with both experimental and theoretical studies. Small, soft Lewis acids (such as Me 3Al) promote endo cycloaddition with the vinyl ether reacting in an s-trans conformation. Most other Lewis acids favor exo cycloaddition due either to their size (such as MAPh) or the conformation they force upon the nitroalkene-Lewis acid complex (such as SnCl4). The s-trans vinyl ether conformation is also favored in these cases, except when phenylcyclohexanol-derived vinyl ethers are used. The s-trans conformation is then disfavored by hard, halogenated Lewis acids (such as SnCl4), and the s-cis conformation is favored.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Seierstad, Mark Jason

Contributors dc:contributor

• Denmark, Scott E.

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI9990133

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84498