published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

A set of mild conditions for the pentafluorophenylation of carbonyl compounds employing copper-bisphosphine catalysis have been developed. The optimised conditions allow access to a wide range of pentafluorophenyl benzyl alcohols in high yields. The reaction of aliphatic aldehydes and particularly electrophilic ketones to give products in moderate yields is also disclosed. An investigation into the reactivity of β-fluoroalkyl-α ,β -unsaturated carbonyl compounds was conducted. Asymmetric copper hydride reduction of β -fluoroalkyl-α , β-unsaturated ketones was found to preferentially give the allylic alcohol product resulting from 1,2 attack in up to 62% ee. Reaction of β-fluoroalkyl-α , β-unsaturated esters under similar conditions gave the product of conjugate reduction in higher enantiomeric excess; up to 99% was observed. Rhodium-catalysed arylation of β -fluoroalkyl-α , β-unsaturated ketones was also found to give the product of direct carbonyl attack. Conditions for the racemic reaction are described along with those for the enantioselective reaction of methyl ketones in up to 74% ee. Ruthenium catalysed arylation of β-fluoroalkyl-α ,β -unsaturated aldehydes employing Me-Bipam as ligand gave the desired secondary allylic alcohols in good yields and good to excellent enantiomeric excesses (14 examples, 76-87% ee).

One microfiche--`Data from crystal structures solved by the author`--in pocket / Bibliography: leaves 214-225 / 225 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1987

Thesis (M.Sc.)--Memorial University of Newfoundland, 2000. / Bibliography: leaves 81-83.

Thesis (Ph. D.)--Rutgers University, 2009. / "Graduate Program in Food Science." Includes bibliographical references (p. 113-126).

published_or_final_version / Biological Sciences / Master / Master of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

No description available.

No description available.