This thesis is mainly focused on the development of new palladium catalyzed transformations using so-called “pincer” complexes. These complexes were applied as catalysts in two important areas of organometallic chemistry: substitution of propargylic substrates by dimetallic reagents; and allylation of aldehydes and imines by allylstannanes. In addition, this thesis includes studies on Lewis acid mediated cyclization reactions of allylsilanes with aldehydes. Pincer complex catalyzed substitution of various propargylic substrates could be achieved under mild conditions using tin and silicon based dimetallic reagents to obtain propargyl- and allenylstannanes and silanes. The regioselectivity of the substitution reaction strongly depends on the steric and electronic effects of the propargylic substrate. According to our mechanistic studies the key intermediate of the reaction is an organostannane (or silane) coordinated pincer complex. DFT modeling studies on the transfer of the trimethylstannyl functionality to the propargylic substrate revealed a novel mechanism, which is based on the unique topology of the pincer-complex catalysts. Our further studies showed that palladium pincer complexes can be employed as efficient catalysts for electrophilic allylic substitution of allylstannanes with aldehyde and imine substrates. In contrast to previous applications for electrophilic allylic substitutions via bis-allylpalladium complexes, this reaction involves mono-allylpalladium intermediates which were observed by 1H-NMR spectroscopy. The last chapter of this thesis is focused on Lewis-acid mediated cyclization of hydroxy functionalized allylsilanes, which afford tetrahydropyran derivatives with a high stereoselectivity.
| Identifer | oai:union.ndltd.org:UPSALLA1/oai:DiVA.org:su-416 |
| Date | January 2005 |
| Creators | Kjellgren, Johan |
| Publisher | Stockholms universitet, Institutionen för organisk kemi, Stockholm : Institutionen för organisk kemi |
| Source Sets | DiVA Archive at Upsalla University |
| Language | English |
| Detected Language | English |
| Type | Doctoral thesis, comprehensive summary, info:eu-repo/semantics/doctoralThesis, text |
| Format | application/pdf |
| Rights | info:eu-repo/semantics/openAccess |
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