Physical Sciences and Mathematics Commons^™

Donor-Acceptor Cyclobutanes And Their Application For Heterocycle Synthesis And Progress Towards Biselide A, Benjamin Machin

Electronic Thesis and Dissertation Repository

The chemistry of cyclobutane-1,1-diester has been investigated with aldehydes and alkyne reaction partners independently of each other. Under Yb(OTf)₃ catalysis donor-acceptor cyclobutanes undergo a formal [4+2] cycloaddition with aldehydes to generate tetrahydropyrans exclusively in a cis disposition. Activated aldehydes were generally well tolerated giving tetrahydropyrans in moderate to good yields (51 - 89%) whereas less reactive congeners gave lower yields (51 - 72%).

All carbon reaction partners were used in BF₃·OEt₂ mediated conditions to afford an unexpected 2,3-dihydrooxepine product resulting from alkynyl addition and rearrangement. Aryl acetylenes were compatible with the reaction conditions and moderate yields …