Cobalt(II) Catalyzed Asymmetric Hydrovinylation of Alkyl- and Trialkylsilyloxy-1,3-Dienes

Cobalt catalysis has become an interest for organometallic and organic chemists over the past forty years as an alternative to more expensive, more toxic, or more unstable known catalysts. The reactions catalyzed by cobalt-complexes range from Diels-Alder and other cyclizations to cross coupling and hydrocyanation. Recently, cobalt has proven to be a capable catalyst to affect the heterodimerization reactions of alpha-olefins with aryl alkenes and 1,3-dienes. The hydrovinylation reaction, the formal addition of a hydrogen atom and an alkene across a pi-system, is an atom economical reaction that allows for the synthesis of value-added products from simple commodity chemicals and feedstock gases. The true power of this methodology can be seen in the asymmetric hydrovinylation, where a chiral cobalt catalyst combined with 1,3-dienes and ethylene allow for 1,4-hydrovinylation to install a new vinyl group in near perfect stereo- and regioselectivity. The work presented herein expands established methodology that introduced 1,4-hydrovinylation of simple linear 1,3-dienes using cobalt (II) (bis-phosphine) dichloride and an organoaluminum co-catalyst to include the 1-vinylcycloalkene and 2-silyloxy-1,3-diene classes of compounds. Also presented in this thesis is the asymmetric hydrovinylation of the 1-vinylcycloalkenes and 2-trialkylsilyloxy-1,3-dienes, and efforts towards the derivitization of the products of these reactions.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

The Ohio State University

Year dc:date

2012

Author dc:creator

• Page, Jordan P.

Contributors dc:contributor

• RajanBabu, T. V.

• Chemistry
• Cobalt
• Hydrovinylation
• Methodology
• Catalysis
• Dienes
• Silyl Enol Ethers

Statement dc:rights

• unrestricted
• This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.

Language dc:language

English

Repository record dc:identifier

http://rave.ohiolink.edu/etdc/view?acc_num=osu1357322022

OAI identifier oai:identifier

oai:etd.ohiolink.edu:osu1357322022