Nuclear Magnetic Resonance Experiments on Acetals. 43. Reversal of Previous Conformational Assignment in 5-Fluoromethylated-5′-Me-1,3-dioxanes

Abstract

Additional n.m.r. investigations on 5-fluoromethylated-5′-Me-1,3-dioxanes have made it necessary for us to reverse the spectral assignments which were forwarded recently (1) in this journal. Thus, the 5-CF2H group prefers the axial position to the extent of ca. 900 cal/mol, whereas the 5-CFH2 group displays a similar preference for the axial position to the extent of ca. 200 cal/mol. An explanation for these unexpected results is advanced. Final structural assignments have been made possible by homo- and heteronuclear double resonance experiments and by ASIS-studies. The observed relative shifts for 5-CFnH3−n and 5-CH3 signals are shown to be normal (e.g. δ(5e) < δ(5a)). Also, the previously reported 4J(F,H) long range couplings follow a classical M-path.