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Transition-Metal-Free Synthesis of Borylated Thiophenes via Formal Thioboration
Hassen Bel Abed1, Suzanne A Blum1
1Department of Chemistry , University of California-Irvine , Irvine , California 92617-2025 , United States.
Abstract:
A simple, regiocontrolled, and transition-metal-free approach to access exclusively 3-borylated thiophene derivatives is reported. The commercially available B-chlorocatecholborane reagent (ClBcat) acts as a carbophilic Lewis acid to activate the alkyne in readily synthesized ( Z)-organylthioenyne substrates. This boron-induced activation initiates the formal thioboration and subsequent sulfur dealkylation, leading to the formation of 3-borylated thiophenes in good yields. The resulting borylated thiophenes are isolable as boronic esters (Bpin) and boronamides (Bdan). These borylated products are amenable to diverse downstream functionalization reactions, i.e., C-C bond formation through cross-coupling, azidation, bromination, and C-H activation.
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