Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis
This thesis outlines the design, synthesis and utilization of phosphaalkene-based ligands for asymmetric catalysis. Transition metal catalysis studies that utilize achiral phosphaalkene-based ligands are reviewed in Chapter 1. In addition, the synthesis and reactivity of phosphaalkenes are briefl...
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ndltd-LACETR-oai-collectionscanada.gc.ca-BVAU.2429-314082014-03-26T03:37:48Z Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis Dugal-Tessier, Julien This thesis outlines the design, synthesis and utilization of phosphaalkene-based ligands for asymmetric catalysis. Transition metal catalysis studies that utilize achiral phosphaalkene-based ligands are reviewed in Chapter 1. In addition, the synthesis and reactivity of phosphaalkenes are briefly introduced in this chapter. The reactivity of a palladium(II) phosphaalkene complex [MesP=CPh(2-py)⋅PdCl₂] bearing the smaller P-Mes substituent compared to the traditional Mes* is described in Chapter 2. This complex was found to be a competent catalyst for the Overman–Claisen rearrangement with yields ranging from 33% to 91%. In Chapter 3, a modular route to a set of chiral phosphaalkene–oxazoline [PhAk–Ox, R′P=CR′′(C(i-Pr-Ox)R₂)] proligands is described. The synthetic route starts from a chiral pool material (L-valine) and generates the P=C bond by a phospha-Peterson reaction. The electronic and steric properties of the proligands (R′, R′′ and R) were modified using this synthetic route. MesP=CPh(C(i-Pr-Ox)Me₂) was thermally polymerized to generate poly(methylenephosphine). The investigation of the coordination chemistry of PhAk–Ox proligands is described in Chapter 4. Rhodium(I) and iridium(I) PhAk–Ox complexes were characterized by X-ray crystallography and NMR spectroscopy. Rhodium(I) PhAk–Ox complexes were found to be active in the asymmetric allylic alkylation of ethyl (1-phenylallyl) carbonate with dimethyl malonate as a nucleophile. The optimal conditions generated products in 37% yield and 66% ee. The investigations of PhAk–Ox ligands in palladium(0) catalyzed allylic alkylation of 1,3-diphenylpropenyl acetate using malonate type nucleophiles are reported in Chapter 5. The structural modification of the ligand through the incorporation of a gem-dimethyl group [MesP=CPh(C(4-i-Pr-5-Me₂-Ox)Me₂)] was needed to optimize yields (73–95%) and enantioselectivities (79–92%). Ring-closing metathesis processes were used to generate enantioenriched carbocycles. To conclude, the results presented in this dissertation represent the highest reported enantioselectivities for a reaction utilizing a phosphaalkene-based ligand. These results also serve as a proof of concept that phosphaalkene ligands can be used in asymmetric catalysis. 2011-02-17T15:22:40Z 2013-02-28 2010 2011-02-17T15:22:40Z 2011-05 Electronic Thesis or Dissertation http://hdl.handle.net/2429/31408 eng University of British Columbia |
collection |
NDLTD |
language |
English |
sources |
NDLTD |
description |
This thesis outlines the design, synthesis and utilization of phosphaalkene-based ligands
for asymmetric catalysis.
Transition metal catalysis studies that utilize achiral phosphaalkene-based ligands are
reviewed in Chapter 1. In addition, the synthesis and reactivity of phosphaalkenes are briefly
introduced in this chapter.
The reactivity of a palladium(II) phosphaalkene complex [MesP=CPh(2-py)⋅PdCl₂]
bearing the smaller P-Mes substituent compared to the traditional Mes* is described in Chapter
2. This complex was found to be a competent catalyst for the Overman–Claisen rearrangement
with yields ranging from 33% to 91%.
In Chapter 3, a modular route to a set of chiral phosphaalkene–oxazoline [PhAk–Ox,
R′P=CR′′(C(i-Pr-Ox)R₂)] proligands is described. The synthetic route starts from a chiral pool
material (L-valine) and generates the P=C bond by a phospha-Peterson reaction. The electronic
and steric properties of the proligands (R′, R′′ and R) were modified using this synthetic route.
MesP=CPh(C(i-Pr-Ox)Me₂) was thermally polymerized to generate poly(methylenephosphine).
The investigation of the coordination chemistry of PhAk–Ox proligands is described in
Chapter 4. Rhodium(I) and iridium(I) PhAk–Ox complexes were characterized by X-ray
crystallography and NMR spectroscopy. Rhodium(I) PhAk–Ox complexes were found to be
active in the asymmetric allylic alkylation of ethyl (1-phenylallyl) carbonate with dimethyl
malonate as a nucleophile. The optimal conditions generated products in 37% yield and 66% ee.
The investigations of PhAk–Ox ligands in palladium(0) catalyzed allylic alkylation of
1,3-diphenylpropenyl acetate using malonate type nucleophiles are reported in Chapter 5. The
structural modification of the ligand through the incorporation of a gem-dimethyl group [MesP=CPh(C(4-i-Pr-5-Me₂-Ox)Me₂)] was needed to optimize yields (73–95%) and
enantioselectivities (79–92%). Ring-closing metathesis processes were used to generate
enantioenriched carbocycles.
To conclude, the results presented in this dissertation represent the highest reported
enantioselectivities for a reaction utilizing a phosphaalkene-based ligand. These results also
serve as a proof of concept that phosphaalkene ligands can be used in asymmetric catalysis. |
author |
Dugal-Tessier, Julien |
spellingShingle |
Dugal-Tessier, Julien Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis |
author_facet |
Dugal-Tessier, Julien |
author_sort |
Dugal-Tessier, Julien |
title |
Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis |
title_short |
Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis |
title_full |
Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis |
title_fullStr |
Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis |
title_full_unstemmed |
Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis |
title_sort |
synthesis of p,n-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis |
publisher |
University of British Columbia |
publishDate |
2011 |
url |
http://hdl.handle.net/2429/31408 |
work_keys_str_mv |
AT dugaltessierjulien synthesisofpnchelatephosphaalkeneoxazolineligandsandtheirapplicationsinasymmetriccatalysis |
_version_ |
1716655857110876161 |