Over the past two decades, homogeneous Au(I) catalysis has been a valuable synthetic tool for activating a series of unsaturated carbon-carbon bonds towards nucleophilic attack. Despite this progress, Au(I/III) redox chemistry has not been well explored. This is largely due to the challenges associated with the high oxidation potential of gold. Hence, the need for an efficient and safe method for Au oxidation.
Herein, a base-assisted diazonium salt activation has been used to facilitate Au redox reactions under mild reaction conditions. This oxidative coupling method afforded functional isoxazolines with good to excellent yields, while the alternative photoactivation method provided trace amounts of the isoxazoline products. This study further broadens the scope of gold redox chemistry. Similarly, cyloporpanol ring opening has been reported under mild chemical condition. This leads to the formation of β-ketones at up to 85% yields.
Furthermore, a series of novel triazole based ruthenium alkylidene complexes are reported. The well-defined complexes were employed to catalyze the cross-metathesis reaction of styrene and a series of coupling partners. Like Grubb II catalysts, complex Ru-TA 2 gave 56% E-olefin in a cross-metathesis reaction. For ring opening metathesis reaction, our catalysts give up to 55% Z-olefin. Although, the results obtained for cross metathesis and ring opening metathesis polymerization are like currently reported yields from Grubbs catalyst, a significant structural modification would further improve the selectivity of the catalysts while also increasing yield.
|Commitee:||Cai, Jianfeng, Bisht, Kirpal, Liu, Ruisheng|
|School:||University of South Florida|
|School Location:||United States -- Florida|
|Source:||DAI 81/11(E), Dissertation Abstracts International|
|Keywords:||2-isoxazolines, Cyclopropanol, Gold catalysis, Metathesis, Olefin, Oximes|
Copyright in each Dissertation and Thesis is retained by the author. All Rights Reserved
The supplemental file or files you are about to download were provided to ProQuest by the author as part of a
dissertation or thesis. The supplemental files are provided "AS IS" without warranty. ProQuest is not responsible for the
content, format or impact on the supplemental file(s) on our system. in some cases, the file type may be unknown or
may be a .exe file. We recommend caution as you open such files.
Copyright of the original materials contained in the supplemental file is retained by the author and your access to the
supplemental files is subject to the ProQuest Terms and Conditions of use.
Depending on the size of the file(s) you are downloading, the system may take some time to download them. Please be