Use of cyanocarbenes for the synthesis of donor-acceptor cyclopropanes

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.]