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Alkynyl‐B(aam) (aam=anthranilamidato) derivatives are readily available bench‐stable compounds that undergo remarkably selective reactions with Bu3SnH in the presence of [Cp*RuCl]4 as the catalyst. The addition follows a stereochemically unorthodox trans‐selective course; in terms of regioselectivity, the Bu3Sn‐ unit is delivered with high fidelity to the C‐atom of the triple bond adjacent to the...