Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Chiral Carbocations as Lewis Acid Catalysts in Diels-Alder Reactions
KTH, School of Chemical Science and Engineering (CHE).
2012 (English)Independent thesis Advanced level (degree of Master (Two Years)), 20 credits / 30 HE creditsStudent thesis
Abstract [en]

Lewis acids can be used as catalysts in different reactions, but the term Lewis acid catalysts often refers to metal salts. Metal complexes have been widely used for asymmetric catalysis. Asymmetric synthesis can however be performed in a metal-free way by using organocatalysis. New Lewis acid catalysts that are more effective, enantioselective and environmental friendly is of interest. This new type of Lewis acid catalysts could for example be of carbocation based character.

The aim of this project was to synthesize chiral carbocations with different degree of sterical hindrance and investigate their catalytic ability in Diels-Alder reactions. It was presumed that the Diels-Alder reactions were going to be performed in an asymmetric way since the carbocation catalysts were achiral.

Two chiral carbocations were synthesized successfully. The first synthesized carbocation, the less sterical hindered compound 8, was formed as a racemic mixture. The second carbocation, compound 16, could be formed as an enatiomeric pure compound. Both carbocations showed catalytic ability in Diels-Alder reactions and compound 8 was comparable with some common Lewis acid catalysts. In general, when using compound 8 as catalyst, higher catalyst amount gave higher conversions. Higher concentrations also gave higher conversions, but up to a certain level. No trend between polarity of different solvents and conversions could be seen. However, an increased temperature leads to faster reactions. The more rigid and sterical hindered compound 16 catalyzed the reactions slower than compound 8. The longer reaction time may indicate that the reaction occurs with higher selectivity, but no method to measure the ee of the product was found.

An attempt to synthesize a third even more sterical hindered chiral carbocation, compound 19, resulted in a product contaminated by impurities that showed a catalytic ability lower than compound 8 and compound 16 in Diels-Alder reactions.

The synthesis and the use of carbocations as Lewis acid catalysts in Diels-Alder reactions seem promising as a new type of catalysts even though there are questions that are still unanswered, e.g. counter ions effects, possible side reactions, selectivity etc.

Place, publisher, year, edition, pages
2012. , 62 p.
Keyword [en]
•Diels Alder •Asymmetric catalysis •Lewis acid •Carbocation •Organocatalys
National Category
Engineering and Technology
Identifiers
URN: urn:nbn:se:kth:diva-156209OAI: oai:DiVA.org:kth-156209DiVA: diva2:765778
Available from: 2014-11-25 Created: 2014-11-25 Last updated: 2014-11-25Bibliographically approved

Open Access in DiVA

fulltext(2160 kB)189 downloads
File information
File name FULLTEXT01.pdfFile size 2160 kBChecksum SHA-512
a59fc851af68a92d8030ae5cd80f48541627170cbc3209fc45512670b64eae6ee083004f80569b63266a9ccd6ef7104c560d0571fe5133f3530bb963e95b67d1
Type fulltextMimetype application/pdf

By organisation
School of Chemical Science and Engineering (CHE)
Engineering and Technology

Search outside of DiVA

GoogleGoogle Scholar
Total: 189 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

urn-nbn

Altmetric score

urn-nbn
Total: 215 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf