Chem Eur JChemPubSocEurope

Supporting Information for 10.1002/chem.201102942

Web Table. Relative energies and calculated 1H NMR data for species in
aRelative energy in kcal mol-1. Geometry visualisation available by activating hyperlink, which requires a Java-enabled browser. Right-click in the Jmol window invokes further commands. Geometries optimized at the ωB97XD/6-311G(d,p)/SCRF(CPCM,solvent=water) level unless otherwise indicated. bGIAO calculation, using continuum solvent model. Link to TMS calibration. c Full details available via the link to the digital repository entry, invoked as dIn CDCl3. Experimental values 5.87, 5.97, 2.24, 2.14 ppm. eVinyl proton. fMethyl protons, averaged over three hydrogens. g@G4C; Repository link for empty cavity hΔΔG298h(host-guest formation from separated components), -11.0 kcal mol-1. iNBO orbitals, and , E(2) interaction energy, 16.0 kcal mol-1. jΔΔG298h -11.3 kcal mol-1. kNBO E(2) interaction energy, 17.3 kcal mol-1. lΔΔG298 -17.0 kcal mol-1. mIntrinsic reaction coordinate connecting transition state 1 and 4. nΔΔG298h -8.4 kcal mol-1. oΔΔG298h -9.1 kcal mol-1 pCrystal structure as reported for or (deposition numbers 822948 and 822949 respectively). The atom connectivity shown is automatically generated from Jmol. qΔΔG298h +4.0 kcal mol-1 rΔΔG298h -3.0 kcal mol-1. sring junction proton. tTerminal methyl. uCentral methyl.
System ΔΔGa 1H NMR shiftsb Repository,
Me21d - 5.92, 5.96;e 2.22, 2.07f to-9359 to-9315
Me21 6.09, 5.94;e 2.57, 2.12f to-9325 to-9332
Me21g h 4.10, 3.51;e 2.39, -2.33f 20110 to-9362
Me22 i 6.62;e 3.79;s 1.97, 1.69f to-9327 to-9334
Me22g j,k 2.82;e 4.16;s 1.76, -1.62f to-5111 to-9314
1 8.42;e 3.89;s 2.48f to-9328 to-9328
1g l 3.07;e 3.90;s 2.83, -0.76f to-5195 to-9313
4m 4.20, 1.81;s 1.64f to-9346 to-9347
4g n 3.54, 1.29;s 1.81, -2.37f to-9371 to-9373
3/5 6.82;e, 4.83;s 1.92, 1.64f to-9338 to-9354
3/5g o 5.73;e; 2.58;s 1.63, -2.09f 20113 to-9361
Me2CBDR 5.60;e 1.61f to-9352 to-9328
Me2CBDR(g,p) q 5.00, 4.49;e 1.23, -2.60f to-5119 to-9335
Me24 6.55;e 2.40;s 1.87;t 1.09u to-9336 to-9336
Me24(g) r 6.72, 5.69;e 1.69, 1.46;s
0.84, -1.00;u 1.76,-1.86t
to-9388 to-9374
TS1 IRC to-9375
TS2 IRC to-9381
TS2g - to-9384