Brown, Michael John (2011) Synthesis, structure and functionalisation of 1,2-diazetidines. PhD thesis, University of Warwick.

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Abstract

The four-membered cyclic hydrazine, 1,2-diazetidine, has received little attention
from the scientific community. This system has useful potential applications in medicine
and synthetic chemistry, but very few compounds of this class are known. This thesis
describes the synthesis, structure and functionalisation chemistry of new simple 1,2-
diazetidine derivatives. Synthetic studies show a Hard−Soft Acids and Bases controlled
ring closure is necessary to effect acceptable to good yields in cyclisations to saturated
N−carboxyalkyl and N−sulphonyl diazetidines. Functionalisation of these systems via
C−H activation was unsuccessful due to protecting group participation. Synthetic studies
toward the parent 1,2-diazetidine molecule (C2N2H6) using chloramine mediated N−N
ring closure or deprotection strategies were also unsuccessful. Further studies show a
wide range of simple 3-alkylidene-1,2-diazetidines and functionalised derivatives are
accessible from commercial materials in two steps using an efficient Cu(I)-catalysed
cyclisation. The scope of this cyclisation method is assessed. Pd(0)-catalysed Heck
chemistry of 3-methylene-1,2-diazetidines allows a stereoselective route to arylated
derivatives in moderate yields. Furthermore, diastereoselective reduction of these
systems provides an efficient route to 1,2-diamines. Structural studies of a range of
synthesised 1,2-diazetidines by X-ray crystallography and dynamic nuclear magnetic
resonance spectroscopy are presented. Together these studies present the potential these
molecules hold in synthetic chemistry.

Item Type:	Thesis or Dissertation (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Hydrazine -- Analysis, Ring formation (Chemistry)
Official Date:	March 2011
Dates:	Date Event March 2011 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Shipman, Mike
Sponsors:	Engineering and Physical Sciences Research Council (EPSRC) ; GlaxoSmithKline
Extent:	ix, 179 leaves : ill., charts
Language:	eng

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