Date of Graduation

2016

Document Type

Dissertation

Degree Type

PhD

College

Eberly College of Arts and Sciences

Department

Chemistry

Committee Chair

Bjorn C G Soderberg

Committee Co-Chair

Patrick S Callery

Committee Member

John H Penn

Committee Member

Jeffrey L Petersen

Committee Member

Brian V Popp

Abstract

Dihydronaphthalenes have been prepared from a ligand controlled gold catalyzed enyne cycloisomerization reaction by using water as an additive. Additionally, four membered rings were obtained in the absence of water under similar conditions. This method also provides excellent yields of substituted dihydroquinolines and dihydrobenzopyrans. Both aliphatic and aromatic terminal alkynes provide the cyclic products under the optimized conditions. The reaction represents a novel method for the synthesis of seven-membered rings with moderate yields.;1,2,3-Triazoles have been utilized as ligands in a number of synthetic transformations. In our attempt to mimicking the porphyrin with 1,2,3-triazole by macrocyclization was unsuccessful due to poor solubility. The intermediates, for both analogs were synthesized by using Click chemistry and a Mitsunobu reaction and are characterized by NMR.;In addition to porphyrin analogs, P,N,N pincer-type ligands featuring a 1,2,3-triazole were synthesized, characterized and used to prepare palladium, nickel and gold complexes. These complexes were characterized by homo and hetero nuclear 1D and 2D NMR spectroscopy and X-ray crystallography. Attempts to use the new pincer complexes in organic transformations were unsuccessful. However, several interesting crystal structures including four-coordinate nickel(II) square planar complexes and a k1- benzoate gold(I) complex in which gold is bound to an oxygen atom of a benzoate were obtained.

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