Fig. 2: Synthesis of iodobicyclo[1.1.1]pentylmethyl thianthrenium reagent 2.
From: Thianthrenium-enabled modular synthesis of bicyclo[1.1.1]pentanes
a, Discovery and optimization of 2. Carbon, grey; hydrogen, white; sulfur, yellow; iodine, purple. b, Computational reaction profile (PBE0-D3/x2c-TZVPall/CPCM(MeCN)) of the photolysis of 1 and subsequent insertion of [1.1.1]propellane, with key dissociation, ISC and phosphorescence rates given. c, The dominant highest occupied and lowest unoccupied natural transition orbital (HONTO and LUNTO) of the S1 state of 1 at the S0 geometry (isovalue, 0.02 a.u.); the σ*(C–I) and σ*(C–S) NBOs, their contributions to the LUNTO, and the LUNTO after projecting out σ*(C–I) and σ*(C–S) contributions are shown for comparison. a15-mmol scale. b5 min. c60 °C. ISC, intersystem crossing; LED, light-emitting diode; DCM, dichloromethane; DMF, N,N-dimethylformamide; ΔG, Gibbs free energy change, ΔE, energy difference; vert., vertical; equil., equilibrium; dissoc., dissociation; phosp., phosphorescence.
