Use this URL to cite or link to this record in EThOS:
Title: Computational insights into organic and organometallic catalysis
Author: Zhang, Xinglong
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2019
Availability of Full Text:
Access from EThOS:
Full text unavailable from EThOS. Please try the link below.
Access from Institution:
This thesis presents computational studies of some catalytic systems in both organic and organometallic chemistry using density functional theory (DFT). With these studies, we show how electronic structure theory such as DFT can complement experimental studies in elucidating and unravelling complex mechanisms. In Chapter 1, we give an overview of the theoretical background governing computational quantum chemistry and electronic structure theories. We then look at how theory is translated to the quantitative study of chemical reactivity and selectivity through simple transition state theory. Chapters 2 and 3 look at organocatalysis. In Chapter 2, we discuss computational work on the oxidant-promoted, hole-catalysed cyclobutanation between two unsymmetrical olefins (Scheme 0 (a)). Chemoselectivity (of reacting olefins), regioselectivity and stereoselectivity (of product formations) were explored. Chapter 3 discusses the mechanistic investigation of a novel bifunctional hydroxyphosphine catalyst, coupling with terminal phenylsilane reductant, in catalytic Staudinger reduction of azide to amine (Scheme 0 (b)). Chapters 4 to 7 look at the catalytic C-H bond functionalisations using transition-metal catalysts. In Chapter 4, we discuss Pd-catalysed δ-selective C(sp3)-H arylation of α-amino acids (Scheme 0 (c)). In Chapter 5 and Chapter 6, we look at the mechanisms underlying Pd-catalysed meta-selective C(sp2)-H allylation using unbiased internal olefin as an allyl surrogate and alkynylation via inverse Sonogashira coupling using trialkylsilylated bromoalkyne, respectively (Scheme 0 (d)). In Chapter 7, we look at using different transition metal catalysts to effect the regiodivergent C(sp2)-H arylation of isoquinolone (Scheme 0 (e)). Chapter 8 gives some concluding remarks regarding the field of computational chemistry in organic and organometallic catalyses and some outlook to the future of chemistry using other computational tools apart from those used in this thesis.
Supervisor: Paton, Robert ; McGrady, John Sponsor: Agency for Science ; Technology and Research ; Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Computational Chemistry