Isolation and structures of two new alkaloids, secodaphniphylline (I) and methyl homosecodaphniphyllate (II), are described. The structure of the latter, established by X-ray analysis of its bromoacetyl derivative, is in full agreement with its chemical and spectral data. The structure of the former was deduced by chemical correlation between I and II. The 2-azabicyclo-[3.3.1]non-1-ene system, an unusually stable anti-Bredt's-rule imine, was formed from II. © 1972.