Use of cyanocarbenes for the synthesis of donor-acceptor cyclopropanes

UNCG Author/Contributor (non-UNCG co-authors, if there are any, appear on document)
David John von Dohlen (Creator)
Institution
The University of North Carolina at Greensboro (UNCG )
Web Site: http://library.uncg.edu/
Advisor
Mitchell Croatt

Abstract: The development of novel reactions is a crucial facet of organic synthesis. Cyclopropanes are a difficult moiety to produce in organic syntheses due to their large ring strain yet can be found in many natural products and are a common moiety in pharmaceuticals, making their accessibility valuable. The use of hypervalent iodonium alkynyl triflates (HIATs) to generate cyanocarbenes in situ provides a novel way of synthesizing cyano-substituted cyclopropanes. A number of novel reactions were carried out by reacting a variety of electron-rich olefins with phenylcyanocarbene to further expand the substrate scope. The cyclopropanation products that were obtained from those reactions were then tested as potential donor-acceptor cyclopropane reagents in a 1,3-dipolar cycloaddition reaction. While several unsuccessful attempts at the reaction were carried out using the vinyl acetate cyclopropanation product, current work in progress on the n-butyl vinyl ether derivative shows promise. Additionally, the ring-opening necessary for a potential dipolar cycloaddition has been shown through the conversion of the vinyl acetate cyclopropane product to ß-cyano-ß-phenylpropanal, expanding upon the very limited synthetic approaches currently available to it and similarly substituted compounds. [This abstract may have been edited to remove characters that will not display in this system. Please see the PDF for the full abstract.]

Additional Information

Publication
Thesis
Language: English
Date: 2024
Keywords
Carbenes, Cyanocarbenes, Dipolar Cycloaddition, Donor-Acceptor Cyclopropanes
Subjects
Organic compounds $x Synthesis
Carbenes (Methylene compounds)
Ring formation (Chemistry)
Cyclopropane

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