Read in a 3D mol or SD file (File -> Open or File -> Recent Files 1) containing the molecule. This needs to have reasonably accurate 3D coordinates. You can obtain such a file from e.g. a crystal structure, or if that is not available, from molecular modelling calculations. Remember, that couplings are very sensitive to the conformation, so you may have to explore several conformations to see which one actually matches.
Calculate NOE's for pairs of atoms
Calculate coupling constants for pairs of atoms