Diastereoselective Synthesis of Cyclopropyl Diboronates via 1,2‐Boronate Rearrangement

Abstract The preparation of polysubstituted cyclopropanes has garnered considerable attention in the field of synthetic chemistry in recent years. The introduction of boron groups into cyclopropane structures enables efficient functional modification of cyclopropane frameworks through downstream derivatization of carbon–boron bonds. Herein, we report an efficient method for the rapid construction of cyclopropyl diboronates from gem ‐bis(boronates) and thianthrenium (TT) salts. This transformation proceeds through a 1,2‐rearrangement of tetra ‐coordinated boron species, delivering 1,2‐diboronate substituted cyclopropanes in high efficiency. Subsequent borate derivatization provides access to highly diastereoselective polysubstituted cyclopropanes. This method offers a scalable and stereocontrolled approach to cyclopropane synthesis and functional diversification, expanding opportunities for the design of complex cyclopropyl architectures in medicinal chemistry, materials science, and synthesis.