Cascarinoids A-C (1-3), a new class of diterpenoid alkaloids with unpredicted conformations, were isolated and structurally characterized from Croton cascarilloides. It was demonstrated that the dispersion interaction might be one of the main contributors that stabilized the folded conformations for compounds 1-3. Compounds 2 and 3 showed moderate immunosuppressive activity against T and/or B lymphocyte cells.