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Reactions tested with the potential σ‐hole catalysts 1–10, with the proposed mechanism for antimony catalyst 1. Substrate 11 (25 mm) was reacted with 12 (27 mm), nucleophiles 13 or 14 (38 mm), and the catalyst (20 mol %) in dry THF at −100 °C; substrate 17 (167 mm) was reacted with 14 (250 mm) and the catalyst (20 mol %) in dry THF at −78 °C, together with 1,4‐bis(trimethylsilyl)benzene (6 mm) as an internal standard. See the Supporting Information for details.
