Memorial University DAI: Transition metal-mediated diastereoselective synthesis of metallophosphinates

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Title	Transition metal-mediated diastereoselective synthesis of metallophosphinates
Author	Zhou, Zhongxin, 1962-
Description	Thesis (Ph.D.)--Memorial University of Newfoundland, 1994. Chemistry
Date	1994
Pagination	421 leaves : ill.
Subject	Chirality; Asymmetric synthesis; Enantiomers; Transition metals
Degree	Ph.D.
Degree Grantor	Memorial University of Newfoundland. Dept. of Chemistry
Discipline	Chemistry
Language	eng
Notes	Bibliography: leaves 256-377
Abstract	New methods and tools have led to optimized ship structure, but poorly designed details persist, leading to fatigue failure. The cost of optimizing all details is prohibitive. Transition metal-mediated diastereoselective synthesis is one of the most important and extensively used methods to create chiraiity at carbon and other heteroatom centres. This thesis focuses on chiral induction from an asymmetric, pseudo-octahedral metal centre in the Arbuzov-like dealkylation of prochiral phosphonites. A series of if-cyclopentadienyl, η5-pentamethylcyclopentadienyl, and η5-indenyl three- legged piano-stool complexes have been studied as chiral auxiliaries. The effects of ligand sphere steric and electronic properties on M* → P optical induction have been examined. -- The synthesis, structure, spectroscopic properties of a series of chiral rf-indenyl cobalt complexes are described. X-ray crystal structure and solution conformational analysis showed that all η5-indenyl complexes have a propensity to distort away from η5 toward if coordination, and that the indenyl ring always has certain conformational preferences with respect to the ligands on the metal. Distortion and conformational preferences of indenyl complexes are fully discussed on the basis of extended Huckel molecular orbital (EHMO) calculations, and fragment molecular orbital (FMO) analysis. -- Arbuzov reactions of η5-indenyl, η5-cyclopentadienyl, and η5-pentamethyIcyclopenta-dienyl cobalt iodide auxiliaries with PR'(OMe)2 (R' = OMe, Ph) proceed via an ionic mechanism to form the corresponding cobaltophosphonates or phosphinates. Ionicintermediates were observed by 1H NMR spectroscopy at ambient temperature in most cases and isolated in some cases. -- The following conclusions can be drawn from the results presented in this thesis: (i) The chiral metal center is essential for stereoselectivity, (ii) The steric requirements of the spectator ligands is crucial in determining chiral induction. The bulkier the spectator ligands, the higher the chiral induction. (iii) The stereochemical properties of the entering phosphonites, PR'(OMe)2 is also important for diastereoselectivity. Large substituent R' result in high diastereoselectivity. (iv) Intramolecular hydrogen bonding plays a significant role in controlling the stereoselectivity in the Arbuzov reaction by restricting population of solution conformations, maximizing the preference of one diastereomer over another.
Type	Text
Resource Type	Electronic thesis or dissertation
Format	Image/jpeg; Application/pdf
Source	Paper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries
Local Identifier	76221203
Rights	The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission.
Collection	Electronic Theses and Dissertations
Scanning Status	Completed
PDF File	(44.62 MB) -- http://collections.mun.ca/PDFs/theses/Zhou_Zhongxin.pdf
CONTENTdm file name	190395.cpd