Cyclopropane-to-organoboron conversion via C–H and C–C bond activation

Abstract

Organoborons have emerged as a class of privileged building blocks in modern organic synthesis, enabling unparalleled molecular diversity and serving as versatile carboxylic acid bioisosteres with profound implications in drug discovery. Concurrently, cyclopropanes have garnered sustained attention as unique synthetic platforms, with their rigid and highly strained three-membered ring structures conferring distinctive steric and electronic properties that facilitate selective C–H and C–C activation processes. The strategic transformation of cyclopropanes into organoborons represents a particularly appealing synthetic approach, offering access to valuable molecular architectures. This review systematically examines the seminal advancements of cyclopropane-to-organoboron conversion over recent years, employing a structured classification based on two fundamental activation modes: C–H borylation and C–C borylation. The review provides in-depth mechanistic elucidation, with particular emphasis on catalytic cycles, key reactive intermediates, and stereodiscrimination processes, thereby offering fundamental insights into the governing principles of these transformations. Looking forward, continued innovation in catalyst design and the exploration of novel reaction pathways are anticipated to significantly expand the synthetic utility and scope of conversions, potentially opening new frontiers in organic synthesis and medicinal chemistry.