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Restricted rotation about the N–S partial double bonds in a bis‐N‐triflyl substituted 3,8‐diazabicyclo[3.2.1]octane derivative 1 has been frozen at low temperature (ΔG≠ = 11.6 kcal mol−1), and the existence of all four rotamers about the two N–S bonds, 3‐in,8‐in, 3‐in,8‐out, 3‐out,8‐in, and 3‐out,8‐out, respectively, proved experimentally by NMR spectroscopy and theoretically by DFT and MP2 calculations...
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