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Stereochemical nversion in Difunctionalized Pillar[5]arenes Nathan L. Strutt, Severin T. Schneebeli, J. Fraser Stoddart* Department of hemistry, Northwestern University, Evanston, L U.S.A.

1 Stereochemical nversion in Difunctionalized Pillar[5]arenes Nathan L. Strutt, Severin T. Schneebeli, J. Fraser Stoddart* Department of hemistry, Northwestern University, Evanston, L U.S.A. stoddart@northwestern.edu Supporting nformation ontents S1. General Methods S2 S2. 1H NMR Spectra of ompounds 2 and 3 S3 S3. Variable Temperature 1H NMR Spectra of 1 S4 6 S4. Variable Temperature 1H NMR Spectra of 2 S7 8 S5. Variable Temperature 1H NMR Spectra of 3 S9 10 S6. 2-D NMR Experiments with 1 S11 14 S7. 2-D NMR Experiments with 2 S15 17 S8. 2-D NMR Experiments with 3 S18 21 S9. Simulated 1H NMR spectra of 1 S22 23 S10. Eyring Plot for 3 S24 S11. X-Ray rystallography of 3 S25 S12. Molecular Mechanics alculations S26 S13. Quantum Mechanical alculations S27 S14. DFT-ptimized Structures and Energies S28 51

2 S1. General Methods Analytical thin-layer chromatography (TL) was carried out using glass plates, precoated with silica gel 60 and fluorescent indicator (Whatman LK6F). The plates were inspected by UV light (254 nm). Flash chromatography was carried out using silica gel 60 (Silicycle) as the stationary phase. Nuclear magnetic resonance (NMR) spectra were recorded on Bruker Avance 500 and 600 MHz spectrometers, with working frequencies of and MHz for 1 H, and and MHz for 13 nuclei, respectively. hemical shifts are reported in ppm relative to the signals corresponding to the residual non-deuterated solvent and coupling constants were recorded in Hertz (Hz). Temperatures for VT 1 H NMR experiments were calibrated using either 100% MeH or 100% ethylene glycol. Simulated 1 H NMR spectra were created using inmr version Single crystal X-ray data was collected on a Bruker Kappa APEX D Diffractometer equipped with a ukα microsource with Quazar optics. Molecular mechanics calculations were performed with the PLS-2005 force field using the program MacroModel software package. alculations were performed with the chloroform GB/SA solvation model. Density functional theory (DFT) calculations were performed with the B3LYP functional using the Jaguar software package. Single point calculations were conducted with the Poisson-Boltzmann continuum-solvation model implemented in Jaguar using either the 6-311G**++ or LAV3P**++ basis set. Geometry optimizations and frequency calculations were conducted with either the 6-31G* or LAVP*basis set. Default grids and SF convergence criteria as implemented in Jaguar were used. S2

3 S2. 1 H NMR Spectra of ompounds 2 and 3 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 +V Hl3 H$ H" H% H# H! H2l2 Hc+d He Ha+b δ (ppm) Figure S1. 1 H NMR (600 MHz, 318 K, Dl 3 ) spectrum of compound 2. H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 +V H Hl3 H! H" H# H$ H2l2 Hb Hc+d Ha He δ (ppm) Figure S2. 1 H NMR (600 MHz, 318 K, Dl 3 ) spectrum of compound 3. S3

4 S3. Variable Temperature 1 H NMR Spectra of 1 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H Temperature (K) δ (ppm) Figure S3. Variable temperature (VT) 1 H NMR (600 MHz, Dl 3 ) spectra of 1. S4

5 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H Temperature (K) δ (ppm) Figure S4. Variable temperature (VT) 1 H NMR (600 MHz, Dl 2 Dl 2 ) spectra of 1. S5

6 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H Ha + Hb Temperature (K) δ (ppm) Figure S5. Variable temperature (VT) 1 H NMR (600 MHz, 4:1 Dl 3 / D 3 D) spectra of 1. S6

7 S4. Variable Temperature 1 H NMR Spectra of 2 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H Temperature (K) δ (ppm) Figure S6. Variable temperature (VT) 1 H NMR (600 MHz, Dl 3 ) spectra of 2. S7

8 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 Temperature (K) Figure S7. Variable temperature (VT) 1 H NMR (600 MHz, Dl 2 Dl 2 ) spectra of 2. S8

9 S5. Variable Temperature 1 H NMR Spectra of 3 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H Temperature (K) δ (ppm) Figure S8. Variable temperature 1 H NMR (600 MHz, Dl 3 ) spectra of 3. S9

10 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H Temperature (K) δ (ppm) Figure S9. Variable temperature (VT) 1 H NMR (600 MHz, Dl 2 Dl 2 ) spectra of 3. S10

11 S6. 2-D NMR Experiments with 1 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 V + + He Hc+d Ha Hb 2D HSQ 233 K Dl3 600 MHz ! (ppm) ! (ppm) Figure S10. Phase-sensitive multiplicity-edited 2-D HSQ spectrum (600 MHz, 233 K, Dl 3 ) of 1 (left). Enlargement of aliphatic section of HSQ spectrum (right). Red crosspeaks indicate H 2 groups and blue crosspeaks indicate H 3 groups. S11

12 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 V + + He Hc+d Ha Hb 2D NESY 228 K Dl3 600 MHz H! H% H$ H# H" (H! Ha) (H% Ha) (H% ) (H# V) (H" ) (H! ) (H" Hc+d) (H$ ) (H" ) (H! Hb) (H% Hb) Hl3 7.0 H (H Ha) (H ) (H Hb) ! (ppm) ! (ppm) Figure S11. 2-D NESY Spectrum (600 MHz, 228 K, Dl 3 ) of 1 (left). Enlargement of the bottom right section of the spectrum (blue box in full spectrum) with annotated crosspeaks (right). S12

13 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 Hc+d He Ha+b V 2D HSQ 348 K Dl2Dl2 600 MHz ! (ppm) ! (ppm) Figure S12. 2-D HSQ Spectrum (600 MHz, 348 K, Dl 2 Dl 2 ) of 1 (left). Enlargement of aliphatic section of HSQ spectrum (right). S13

14 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 Hc+d He V Ha+b 2D NESY 350 K Dl2Dl2 600 MHz 4.0 H (H ) (H Ha+b) (H$ He) (H$ V) 5.0 H$ (H% Ha+b) 6.6 H% H! H# (H# Hc+d) (H! Ha+b) (H$ ) H" (H" Hc+d) (H! ) (H# V) (H" ) (H" ) ! (ppm) ! (ppm) Figure S13. 2-D NESY Spectrum (600 MHz, 350 K, Dl 2 Dl 2 ) of 1 (left). Enlargement of the bottom right section (blue box in full spectrum) with annotated crosspeaks (right). S14

15 S7. 2-D NMR Experiments with 2 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 V He Hc+d Ha+b 2D HSQ 318 K Dl3 600 MHz ! (ppm) ! (ppm) Figure S14. 2-D HSQ Spectrum (600 MHz, 318 K, Dl 3 ) of 2 (left). Enlargement of aliphatic section of HSQ spectrum (right). S15

16 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 H# H! Hl3 H$ H" H% 2D NESY 318 K Dl2Dl2 600 MHz ( H") V + Hc+d Ha+b He (V H#) ( H$) (He H$) (Ha+b H!) (Ha+b H%) ( H!) (Hc+d H#) (Hc+d H") ! (ppm) ! (ppm) Figure S15. 2-D NESY Spectrum (600 MHz, 318 K, Dl 3 ) of 2 (left). Enlargement of the top left section (blue box in full spectrum) with annotated crosspeaks (right). S16

17 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 Hc+d V He Ha+b 2D HSQ 298 K Dl2Dl2 600 MHz ! (ppm) ! (ppm) Figure S16. 2-D HSQ Spectrum (600 MHz, 298 K, Dl 2 Dl 2 ) of 2 (left). Enlargement of the aliphatic section of the HSQ spectrum (right). S17

18 S8. 2-D NMR Experiments with 3 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 V + Hc+d Hb Ha He 2D HSQ 300 K Dl3 600 MHz ! (ppm) ! (ppm) Figure S17. 2-D HSQ Spectrum (600 MHz, 300 K, Dl 3 ) of 3 (left). Enlargement of aliphatic section of HSQ spectrum (right). S18

19 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 V + Hc+d Hb Ha He 2D NESY 300 K Dl3 600 MHz H$ H# H" Hl3 H! (H$ V) (H$ He) (H$ ) (H" ) (H# V) (H" ) (H" Hc+d) (H# Hc+d) (H! Ha) (H! Hb) (H! ) H (H Hb) (H ) (H Hb) ! (ppm) ! (ppm) Figure S18. 2-D NESY Spectrum (600 MHz, 300 K, Dl 3 ) of 3 (left). Enlargement of the bottom right section (blue box in full spectrum) showing annotated crosspeaks. S19

20 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 Ha+b Hc+d He V 2D HSQ 368 K Dl2Dl2 600 MHz ! (ppm) ! (ppm) Figure S19. 2-D HSQ Spectrum (600 MHz, 368 K, Dl 2 Dl 2 ) of 3 (left). Enlargement of the aliphatic section of the HSQ spectrum (right). S20

21 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 Ha+b Hc+d He V 2D NESY 348 K 3.0 Dl2Dl2 600 MHz H# (H# Hc+d) (H# ) (H# V) H$ (H$ He) (H$ ) (H# V) H" (H" Hc+d) (H" ) (H! Ha+b) (H" Hc+d) 6.9 H! H (H Ha+b) (H ) (H! ) ! (ppm) ! (ppm) Figure S20. 2-D NESY Spectrum (600 MHz, 348 K, Dl 2 Dl 2 ) of 3 (left). Enlargement of bottom right section (blue box in full spectrum) showing annotated crosspeaks (right). S21

22 S9. Simulated 1 H NMR Spectra of 1 Dynamic 1 H NMR simulations were conducted for protons and on the methylene bridges of 1 using inmr (version 3.2.1). The magnetic field, B 0, for the simulated spectra was set to a frequency of for 1 H, while the experimental spectra were conducted using a B 0 of MHz. Figures S20 - S24 contain the experimental 1 H NMR spectra for the aliphatic portion of 1 directly above the simulated spectra at the same temperature. T = 328 K k = 119,000 s -1 Experimental Simulated δ (ppm) Figure S21. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 328 K, Dl 3 ) of the aliphatic portion of 1. T = 298 K k = 19,800 s -1 Experimental Simulated δ (ppm) Figure S22. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 298 K, Dl 3 ) of the aliphatic portion of 1. S22

23 T = 268 K k = 1057 s -1 Experimental Simulated δ (ppm) Figure S23. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 268 K, Dl 3 ) of the aliphatic portion of 1. T = 238 K k = 33 s -1 Experimental Simulated δ (ppm) Figure S24. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 238 K, Dl 3 ) of the aliphatic portion of 1. T = 218 K k = 6.0 s -1 Experimental Simulated δ (ppm) Figure S25. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 218 K, Dl 3 ) of the aliphatic portion of 1. S23

24 S10. Eyring Plot for 3 Dynamic 1 H NMR simulations were conducted for protons and on the methylene bridges of 3 using the same method described for the simulation of the dynamic 1 H NMR of 1. The rates obtained through the 1H NMR simulations were used to generate an Eyring plot (Figure S26). The Eyring plot was used to calculate ΔH and ΔS for the inversion process in 3. ln (k / T) = ( ± 133.6) + (27.59 ± 0.44) R 2 = H = 18.2 ± 0.3 kcal mol -1 S = 7.6 ± 0.9 cal mol -1 K -1 Figure S26. Eyring plot of the stereochemical inversion process of 3 using simulated 1 H NMR spectroscopic data to determine the rate of the process at multiple temperatures. The equation of the linear curve was used to calculate ΔH and ΔS for this process. S24

$Data was collected at 100 K on a Bruker Kappa APEX D Diffractometer equipped with a ukα microsource with Quazar optics.$

25 S11. X-Ray rystallography of 3 a) Methods. Single crystals of 3 were grown by slow evaporation of H 2 l 2. Data was collected at 100 K on a Bruker Kappa APEX D Diffractometer equipped with a ukα microsource with Quazar optics. The SQUEEZE function of PLATN was used to remove the contribution of disordered solvent molecules to the data. b) rystal Parameters. Formula: 43 H 44 Br 2 10, orange block, mm 3, monoclinic, space group P2 1 /n; a = (3), b = (9), and c = (7) Å; β = (2) ; V = (4) Å 3 ; T = 100(2) K, Z = 8, ρ calc = g cm 3, µ(u Kα) = mm 1, F(000) = 3616; independent measured reflections = 92,194; R 1 = and wr 2 = for independent observed reflections [2θ 124, > 2σ ()]. D# Figure S27. X-Ray crystal structure of 3 with thermal ellipsoids shown at a 50% probability level. atoms are black, atoms are red, Br atoms are gold, toms are white. S25

26 S12. Molecular Mechanics alculations Molecular mechanics coordinate scans were performed with MacroModel to determine approximate structures for the transition states between intermediate conformations. The coordinate scans were conducted by rotating the respective aromatic unit at 1 intervals over 180 through the pillar[5]arene cavity. The PLS 2005 energies of the highest energy structures of the coordinate scans (approximate transition states) are listed in Table S1. The molecular mechanics calculations were conducted with the chloroform GB/SA solvation model implemented in Macromodel. Due to the symmetry of the system, the reverse pathways involving enantiomers of the transformations listed were assumed to have the same transition state and energy barrier, e.g. the tranformation of conformer 1 to conformer 1 a1 would have a transition state which is the enantiomer of the transformation of conformer 1* to conformer 1 a1 *. Table S1. PLS 2005 energies of approximate transition states. Transformation (1 st conformer to 2 nd conformer) Relative PLS 2005 Energy (in Hl 3 ) (kcal mol -1 ) 1 to 1 a a1 to 1 b b1 to 1 b3 * a3 to 1 b a3 to b1 to 1 b6* b6 to 1 a to 1 a a2 to 1 b a2 to 1 b a3 to 1 b S26

27 S13. Quantum Mechanical alculations Density functional theory (DFT) calculations were performed with the B3LYP exchangecorrelation functional using the Jaguar software package. Geometry optimization and frequency calculations were conducted with either the 6-31G* or LAVP* basis set. Table S2 lists the lowest calculated vibrational frequency and zero point energies for each intermediate conformer and transition state. Single point calculations (Table S2) were conducted with a Poisson-Boltzmann continuum-solvation model using either the 6-311G**++ or LAV3P**++ basis set. Default grids and SF convergence criteria as implemented in Jaguar were used. Table S2. DFT calculated properties for intermediate conformers and transition states ntermediate onformer Single Point Energy (Hartrees) Zero Point Energy (Hartrees) Total Energy (Hartrees) Energy Relative to onformer 1 (kcal mol -1 ) a b b6 * a3 * Transition State Single Point Energy (Hartrees) Zero Point Energy (Hartrees) Total Energy (Hartrees) Energy Relative to onformer 1 (kcal mol -1 ) TS 1 (1 / 1 a2 ) TS 2 (1 a2 / 1 b1 ) TS 3 (1 b1 / 1 b6 *) TS 4 (1 b6 * / 1 a3 *) TS 5 (1 a3 * / 1*) S27

28 S14. DFT ptimized Structures and Energies onformer 1 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H S28

12.2848710770 6.2690882188 4.3156132825 H 11.9133715281 6.5749348792 3.3453849315 13.0744474852 7.1325033421 5.0805441806 12.8608760544 8.8956311039 3.4710235656 H 13.1934080641 8.3082570677 2.

8174379633 7.7014137766 H 12.2043614080 1.8285537152 7.7788759201 11.1687239303 4.0328894345 3.8736866403 H 10.5203708996 3.4165258238 4.5035362013 H 10.5258302266 4.6226410473 3.2135326080 12.

29 H H H H H H H H H H H H H H H H H H H Figure S28. Side view (left) and top view (right) of the DFT optimized structure for 1. S29

30 onformer 1 a2 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*]= Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H S30

13.5940011795 8.8645462537 3.4348501384 H 13.9890389473 8.1922357795 2.6609119921 H 14.1109136665 9.8253099385 3.3744021355 H 12.5211297518 9.0212015706 3.2557867520 11.8528056001 3.0590246553 7.

7541997735 4.1768200821 H 10.7101966415 4.9391272744 2.9014355141 12.0891109832 3.2896992570 2.9287287721 13.1658335755 1.1084620223 2.8606758390 13.8848600579 1.4558302360 1.7105165464 13.

31 H H H H H H H H H H H H H H H H H H Figure S29. Side view (left) and top view (right) of the DFT optimized structure for 1 a2. S31

32 onformer 1 b1 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S32

11.4197105602 3.3987970170 7.6213910853 H 11.0104773077 4.2263274516 8.2168549679 H 12.4258519086 3.1589424798 7.9928305829 H 10.7772755188 2.5222276727 7.7352091132 11.2516015118 4.2497559724 3.

33 H H H H H H H H H H H H H H H H H Figure S30. Side view (left) and top view (right) of the DFT optimized structure for 1 b1. S33

34 onformer 1 b6 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H S34

12.8920568086 3.7510189884 1.4845524861 12.9856938406 2.3609328768 1.3216946314 12.2636790688 1.5564786934 2.2058128249 H 12.3190884633 0.4810968567 2.0758245155 13.7165156979 5.9166087706 0.

3962099650 3.0195845397 H 10.1692314645-0.4624625203 4.7862119238 H 11.8256848247-0.4660926851 4.1185881198 12.1578392268 4.2956965326 2.5356742512 H 12.1301700868 5.3696740327 2.6840629902 11.

35 H H H H H H H H H H H H H H H H H H Figure S31. Side view (left) and top view (right) of the DFT optimized structure of 1 b6 * S35

36 onformer 1 a3 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S36

8.5870023675 8.1086386279 2.9632999962 H 7.7504778125 8.1266679653 3.6758696452 H 8.1840227831 8.1568967591 1.9417555085 H 9.2245492302 8.9784213618 3.1381235566 12.0930273428 4.0338755995 2.

37 H H H H H H H H H H H H H H H H H Figure S32. Side view (left) and top view (right) of DFT optimized structure 1 a3 *. S37

38 Transition state in the conversion of conformer 1 to 1 a2 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H S38

H 19.2988225159 1.9996419698 11.3352784773 H 19.2262402073 3.3081783403 12.5483968748 H 20.2022478757 1.8471523995 12.8699002072 26.2256590348 1.1211925579 8.6521644762 H 26.7464131075 1.6418856335 9.

4740967466 10.7912828833 22.4549107059-1.5913905286 8.6639281977 22.9723478566-2.4511663937 6.4425874876 21.6131201388-2.5196024556 6.1087949417 20.6864583555-2.1467887094 7.0883713613 H 19.

39 H H H H H H H H H H H H H H H H H H Figure S33. Side view (left) and top view (right) of the optimized transition state between conformers 1 and 1 a2. S39

40 Transition state in the conversion of conformer 1 a2 conformer 1 b1 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*]= Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H S40

H 15.0619680197 7.4109031418 4.2548229779 H 15.4806794441 8.7096026275 5.4083299607 H 13.7692578406 8.3763722693 5.0245291246 11.6293033844 1.6197810170 7.3624004208 H 11.3452317355 2.1237631479 8.

0899215694 3.5693740383 12.1620771846 3.3751429512 2.9456197557 13.1009106663 1.2593649560 2.1703618620 13.8187593509 1.9210794643 1.1634497960 13.6484032436 3.3021959034 1.0275205653 H 14.

41 H H H H H H H H H H H H H H H H H H Figure S34. Side view (left) and top view (right) of the optimized transition state between conformers 1 a2 and 1 b1. S41

42 Transition state in the conversion of conformer 1 b1 conformer 1 b6 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S42

9.1129771483 5.3030279806 0.1478654630 H 8.1401389302 5.8126330373 0.1863093443 H 9.0752701823 4.5214250130-0.6234692317 H 9.8882096258 6.0272851293-0.1116543661 10.5143798557 3.5939361241 3.

2871737267 1.4961510790 13.8799901421 2.3931899818 2.2942848966 H 14.9275342438 2.6768170343 2.3353410751 10.4180754414-0.3635399788 0.4434708762 H 9.8828294952-0.6682386183 1.3525945488 H 10.

43 H H H H H H H H H H H H H H H H H Figure S35. Side view (left) and top view (right) of the optimized transition state between conformers 1 b1 and 1 b6 *. S43

44 Transition state in the conversion of conformer 1 b6 * conformer 1 a3 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H S44

6.3358349271 5.8969016558 5.2829189988 7.2533144730 6.4019173121 4.3557011332 H 6.9735386127 7.2831972362 3.7894844784 6.0637513842 3.1622310067 7.7153652619 H 6.2787516726 2.2871748717 7.

8090780763 2.1977452148 H 9.0431094016 8.3737278305 3.4618206591 7.9655176272 4.1997444418 5.8827208834 H 8.2694543700 3.3623385768 6.5015808713 8.5228861722 5.8460911921 4.2207056900 5.0141995973 6.

45 H H H H H H H H H H H H H H H H H H Figure S36. Side view (left) and top view (right) of the optimized transition state between conformers 1 b6 * and 1 a3 *. S45

46 Transition state in the conversion of conformer 1 a3 * conformer 1* Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = Hartrees (oordinates in Ångströms) atom x y z H H H H H H H H H H H H H H H H H H H H H H H H H H H H S46

H 8.0221186996 6.8531356484-0.3263733653 8.8710505112 1.6944451524 5.0090359390 H 8.4682188179 0.9564071848 4.3037861693 H 8.0558269657 2.0583829199 5.6493241693 H 9.6317299747 1.2115796276 5.

2436253072 2.0525587645 13.9220059138 3.1301546014 6.7813210953 H 14.4829002410 3.9156995415 6.2601849669 H 14.4932018897 2.7889693149 7.6468530005 H 12.9578615278 3.5322631915 7.1170356639 11.

47 H H H H H H H H H H H H H H H H H H Figure S37. Side view (left) and top view (right) of the optimized transition state between conformers 1 a3 * and 1*. S47

48 Ground state of 3 Energy [B3LYP (solvation)/ LAV3P**++// B3LYP/ LAVP*] = Hartrees (oordinates in Ångströms) atom x y z Br Br H H H H H H H H H H H H H H H H H H H H S48

H 5.3541970291 16.8956085200 14.2149801759 H 6.7526472167 17.2858038278 13.1739049768 H 5.0960599631 17.6625979769 12.6221160077 1.6887469720 18.0349706516 10.9209259252 H 0.7902398120 17.

6792254838 21.5811463929 9.2578938773 H 6.5398832487 21.0049660658 10.5078997373-2.5243658719 22.8925056571 14.5366440332 H -2.9456260953 22.0633730573 15.1176913550 H -3.2612475773 23.6940021794 14.

49 H H H H H H H H H H H H H H H H H H H H H H H H Figure S38. Side view (left) and top view (right) of the optimized ground state of 3. S49

50 Assumed highest energy transition state of 3 Energy [B3LYP (solvation)/ LAV3P**++// B3LYP/ LAVP*] = Hartrees (oordinates in Ångströms) atom x y z Br Br H H H H H H H H H H H H H H H H H H H H S50

1.6107608701 17.2651877200 7.1858705487 H 2.1832209990 16.5401073462 7.7774904081 H 1.1026672888 16.7428852410 6.3714207694 H 0.8630477018 17.7422538705 7.8331740593 0.5775475650 17.5880204997 12.

5061255513 3.1451137900 H -1.7968956318 20.4141879348 3.3318649014 H -0.7261847005 20.1742517135 4.7412475280 2.5755519810 24.6421369145 11.6483585252 H 3.4317487933 24.4686400960 12.3162544643 H 2.

51 H H H H H H H H H H H H H H H H H H H H H H H H Figure S39. Side view (left) and top view (right) of the highest energy transition state of 3. S51

Supporting Information for. an Equatorial Diadduct: Evidence for an Electrophilic Carbanion

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