The Gabriel amine synthesis is a classic method for the preparation of primary amines. In this textbook reaction, potassium phthalimide reacts with alkyl halides to afford N-alkylphthalimides, which can be hydrolyzed or hydrazinolyzed to primary amines (Scheme 1A). Among the medicinal chemistry community, there is a widespread interest in the synthesis of bioisosteres incorporating higher fraction sp -character. Bicyclo [1.1.0]butanes (BCBs) have emerged from obscurity as strained laboratory curiosities to the limelight as versatile linchpins for the construction of sp 3 -rich molecules. Moreover, BCBs have been used as covalent reactive groups in biochemical tool compounds. Recently, we disclosed a general reaction between iodo-bicyclo [1.1.1]pentanes (BCPs) and nucleophiles to yield substituted BCBs 6 , building from a prior observation by Wiberg. Such iodo-BCPs can be prepared in one step from commercial acid-BCPs by a modification of the Gandelman photo-Hunsdiecker reaction. Under thermal conditions, iodo-BCPs react with primary and secondary amines, thiols, and sulfinates as nucleophiles to afford substituted BCB compounds (Scheme 2B). Distal to the iodide, a bridgehead electron-withdrawing group such as carboxamide or ester seems to be required. Herein, we disclose that potassium phthalimide reacts with iodo-BCPs 2 in polar aprotic solvents to form aminomethyl-BCBs 3. Hydrazinolysis of 3 leads to primary amines 4 (Scheme 2C). Scheme 1. Gabriel amine synthesis applied to BCP to BCB transformation.