Some organometallic chemistry of cycloalkyl systems

Wells, Adam Patrick (1992). Some organometallic chemistry of cycloalkyl systems PhD Thesis, School of Molecular and Microbial Sciences, The University of Queensland. doi:10.14264/uql.2015.578

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Author Wells, Adam Patrick
Thesis Title Some organometallic chemistry of cycloalkyl systems
School, Centre or Institute School of Molecular and Microbial Sciences
Institution The University of Queensland
DOI 10.14264/uql.2015.578
Publication date 1992-01-01
Thesis type PhD Thesis
Supervisor W. Kitching
Total pages 184
Language eng
Subjects 03 Chemical Sciences
Formatted abstract
The mechanism of palladium(II) functionalization of various cycloalkanone oximes has been investigated. It was found that with 2,2-disubstituted cyclohexanone oximes, palladium inserted into methyl groups exclusively in preference to allyl-, and benzyl-groups. Oximes without a methyl group in an equatorial orientation, and cycloheptanone and cyclooctanone oximes, all formed a presumed polymeric species which was not fully characterized. Large primary and secondary deuterium kinetic isotope effects (--4 and ~1.2 respectively) were measured in the palladium functionalization of the 2,2-dimethylcyclohexanone oxime system.

The mechanism of palladium(II) mediated demercuration of various cycloalkyland cycloalkylmethylmercuric chlorides has been found to change as a function of ring size. The mechanism for demercuration in the cyclohexylmethyl system, which involves the elimination/readdition of [HPdX], was established by extensive deuterium labelling experiments, and replaces a previously proposed mechanism. The cyclooctyland cyclooctylmethyl systems exhibit a different mechanism involving carbocation formation, while the cycloheptyl- and cycloheptylmethyl systems show evidence of a blend of both mechanisms.

The reactivities of six to nine membered ring cycloalk-1-enylsilanes and 1,2- epoxycycloalkylsilanes have been investigated following reports of unusual mechanisms leading to trans-cyclooctenes. Careful examination of the products show that these reactions have a marked dependence on ring size. The mechanisms of some of these reactions have been clarified by the use of deuterium labelled analogues, demonstrating the unimportance of several proposed mechanisms.
Keyword Cycloalkanes
Organometallic chemistry

Document type: Thesis
Collection: UQ Theses (RHD) - UQ staff and students only
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