The present disclosure provides compounds of Formulae (I-A), (II′), (III-A), (IV′), and (V-A), wherein the compounds are derived from or based on yohimbine. The provided compounds may be useful in treating or preventing a disease (e.g., proliferative disease, cancers, inflammatory diseases, autoimmune diseases, and infectious diseases) in a subject in need thereof. The present disclosure provides methods of preparing compounds of Formulae (I-A), (II′), (III-A), (IV′), and (V-A). Also provided are pharmaceutical compositions, kits, methods, and uses that include or involve a compound described herein.