Nickel-catalyzed cross-couplings via activation of carbon-oxygen and carbon-nitrogen bond
| Author(s) | Xu, Jianyu | |
| Date Accessioned | 2023-04-26T16:56:03Z | |
| Date Available | 2023-04-26T16:56:03Z | |
| Publication Date | 2020 | |
| SWORD Update | 2023-03-01T14:04:16Z | |
| Abstract | This dissertation focuses on nickel-catalyzed cross-couplings via carbon– oxygen and carbon–nitrogen bond activation. These methods transform readily available benzylic alcohol derivatives (in enantioenriched form) and alkyl amine derivatives into high-value products. ☐ Chapter 1 describes a nickel-catalyzed stereospecific vinylation of tertiary benzylic carboxylates. Under our practical conditions, an inexpensive, air-stable nickel precatalyst Ni(acac)2·xH2O is used as the sole catalyst, and exogenous ligand is not required. A variety of styrenyl and alkyl vinyl boronates are tolerated in high yields and stereochemical fidelity. Worth noting, this method works with simple phenyl- substituted benzylic carboxylates, as well as naphthyl-substituted substrates. ☐ Chapter 2 describes a nickel-catalyzed stereospecific arylation of tertiary benzylic carboxylates. In the presence of catalytic Ni(OAc)2·4H2O and a stilbene, phenyl-substituted benzylic carboxylates undergo efficient transformation to highly enantioenriched products with diaryl quaternary stereocenters. This method overcomes the long-standing “Naphthyl Requirement” in this field. All-carbon quaternary stereocenters are formed in high yields and high stereochemical fidelity. ☐ Chapter 3 describes a nickel-catalyzed deaminative cyanation of Katritzky pyridinium salts. A Ni/Xantphos catalyst system was developed to efficiently transform alkyl amines to corresponding alkyl nitriles via C–N bond activation. This method tolerates broad scope, and even performs well in late-stage functionalization, which may give a potentially useful tool in the drug discovery synthesis toolbox. | |
| Advisor | Watson, Mary P. | |
| Degree | Ph.D. | |
| Department | University of Delaware, Department of Chemistry and Biochemistry | |
| DOI | https://doi.org/10.58088/pe20-cs23 | |
| Unique Identifier | 1377503059 | |
| URL | https://udspace.udel.edu/handle/19716/32681 | |
| Language | en | |
| Publisher | University of Delaware | |
| URI | https://login.udel.idm.oclc.org/login?url=https://www.proquest.com/dissertations-theses/nickel-catalyzed-cross-couplings-via-activation/docview/2785249551/se-2?accountid=10457 | |
| Keywords | Naphthyl requirement | |
| Keywords | Stereospecific vinylation | |
| Keywords | Ni(acac)2·xH2O | |
| Title | Nickel-catalyzed cross-couplings via activation of carbon-oxygen and carbon-nitrogen bond | |
| Type | Thesis |