Employment of Palladium Pincer Complex Catalysts and Lewis Acids for Synthesis and Transformation of Organometallic Compounds

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 propargyland 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 bisallylpalladium complexes, this reaction involves mono-allylpalladium intermediates which were observed by H-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. © Johan Kjellgren ISBN 91-7155-026-7 Intellecta DocuSys AB