Supporting Information. Synthesis, resolution and absolute configuration of chiral 4,4 -bipyridines

Supporting Information Synthesis, resolution and absolute configuration of chiral 4,4 -bipyridines Victor Mamane,* a Emmanuel Aubert, b Paola Peluso, c and Sergio Cossu d a Laboratoire SRSMC UMR CRS 7565, ancy Université, 5456 Vandoeuvre-les-ancy, France. b Laboratoire CRM 2 UMR CRS 736, ancy Université, 5456 Vandoeuvre-les-ancy, France. c Institute of Biomolecular Chemistry, UOS of Sassari, C..R., 71 Sassari, Italy. d Dipartimento di Scienze Molecolari e anosistemi, Università Ca' Foscari Venezia, 3123 Venezia, Italy. COTET victor.mamane@srsmc.uhp-nancy.fr Copies of MR spectra of compounds 2-5 S-2 ECD spectrum of 5b-M S-13 Details on the XRD analyses S-14 Details on the theoretical calculations S-16 - Energy barriers of racemisation S-16 - Comparison of experimental and calculated ECD spectra S-4 S-1

S-2 Br Br 1 2 2 ppm (t1). 5. 1. 5 8.7 8.45 7.253..92 1.4 5.46 ppm (t1) 5 1 15 1 2 3 4 5 6 7 8 149.994 149.963 147.157 141.945 136.31 135.645 129.15 128.165 128.125 122.831 77.676 77.41 76.46

1 Br I 3 2 I Br 8.992 8.798 7.267. 6 5 4 3 2 1 1..97 1. ppm (t1) 5.. 156.17 152.49 151.434 12.175 96.64 77.634 77. 76.365 4 3 2 1 ppm (t1) 15 1 5 S-3

S-4 4a ppm (t1). 5. 1. 5 1 15 8.822 8.326 7.262 7.228 7.198 7.145 7.115 7.86 6.62 6.591..98 1. 1.37 2. 2.5 ppm (t1) 5 1 15 1 2 3 4 5 6 15.357 149.215 144.412 137.545 135.277 128.819 128.167 127.971 123.33 77.58 77. 76.492 Br Br 1 2 3 4 5 6 7

S-5 4b ppm (t1). 5. 1. 5 1 15 8.779 8.318 7.268 6.686 6.642 6.596 6.552 3.763..97.98 4.19 3.33 ppm (t1) 5 1 15 5 1 159.481 149.974 149.313 144.53 137.319 13.66 127.727 123.219 113.44 77.58 77. 76.492 55.212 Br Br MeO OMe 1 2 3 4 5 6

S-6 4c ppm (t1). 5. 1. 5 1 15 2 25 3 35 8.777 8.39 7.264 7.224 7.216 7.182 7.146 7.138 6.683 6.649 6.61 6.334 6.328 6.325 6.321 6.319 6.314 6.39 3.47.97 1. 1.7 2.2.99 3.38 ppm (t1) 5 1 15 1 2 3 4 5 156.169 15.945 149.885 144.98 131.436 129.734 123.938 12.11 19.991 54.384 Br Br OMe MeO 1 2 3 4 5 6

S-7 4d ppm (f1). 5. 5 1 15 2 25 8.847 8.328 7.26 7.156 7.114 6.598 6.556 1..98 2.3 2.2 ppm (f1) 5 1 15 5 1 15 2 15.875 149.162 149.113 144.215 136.299 134.87 133.674 13.116 128.448 Br Br Cl Cl 1 2 3 4 5 6

5 4 6 7 3 2 1 Br 4e 8 9 Br ote: MR analysis shows the presence in small amount of a minor conformer (about 8% according to the peak integration). Indeed, the GC analysis shows only one product. The presence of two conformers is expected due to the rotation along the aphtyl Pyridine bond. S-8

S-9 ppm (t1). 5. 1. 1 2 3 4 5 6 7 8.979 8.894 8.643 8.385 8.272 8.226 7.635 7.621 7.63 7.589 7.42 7.379 7.256 7.234 7.22 6.987 6.982 6.952 6.947 6.912 6.97 6.711 6.667 6.467 6.461 6.433 6.425 6.418 6.39 6.384 6.163 6.127 6.122 6.86 5.955 5.914 5.379 5.374 5.344 5.339 1.16 1.3 1..92 1.1 1.1 1.4 2.29.8.7.7.6.8.8.8 ppm (t1) 5 1 15 1 2 3 4 5 151.51 15.18 145.716 135.417 133.548 132.321 131.334 128.786 127.453 127.261 126.87 125.611 124.345 123.373

S-1 4f ppm (t1). 5. 1. 5 1 8.756 8.435 7.254 7.238 7.199 7.161 7.26 7.13 7.3 6.986 6.799 6.756 6.546 6.53 4.48 6.6 2.1 2..9.89 ppm (t1) 5 1 15 5 1 153.8 15.87 149.133 147.96 147.133 144.363 129.614 129.411 128.542 124.86 123.567 121.861 Br Br 1 2 3 4 5 6 7 8 9 1 11 12 13 14 15 16

S-11 5a ppm (t1). 5. 1. 5 1 8.841 8.829 7.316 7.293 7.259 7.241 7.23 7.168 7.163 7.138 7.131 2.3 3.44 2. ppm (t1) 5 1 15 1 2 3 4 15.653 147.667 131.583 129.243 128.416 121.648 121.155 12.367 97.419 83.55 77.58 77. 76.492 Br Br 1 2 3 4 5 6 7

S-12 5b ppm (t1). 5. 1. 1 2 3 4 8.857 8.799 7.258 4.195 4.114 2. 9.66 ppm (t1) 5 1 15 5 1 15 2 15.172 149.822 147.748 121.896 12.312 98.175 79.71 77.24 71.638 71.568 7.17 69.51 62.894 Br Br 1 2 3 4 5 6 Fe Cp Fe

ECD spectrum of 5b-M S-13

Details on the XRD analyses: Bipyridine 2 ORTEP plot of 2. Thermal ellipsoids set at 5% probability and hydrogen atoms shown as sticks. Bipyridine 3 The crystal structure of 3 (2 nd eluted peak) was solved in P1 space group. The Flack parameter introduced as an inversion twin population refined to.269(6), the absolute configuration being P. The R 1 values were.496 (I > 2σ(I)) and.538 (all data). The wr(f 2 ) values were.1481 (I > 2σ(I)) and.1522 (all data). The goodness of fit on F 2 was 1.2. In this model three of the four crystallographically independent molecules, display C-Halogen bonds lengths in between C-Br (1.89Å) and C-I (2.9Å) bond lengths; moreover, corresponding bromine atoms display relative small atomic displacement parameters whereas iodine atoms display relative large ADP values. This indicates that three of these four molecules are disordered. The final model is then built by considering that these three sites are occupied by 3-P molecules having different orientations; the validity of this model is assessed by the significant decrease of the wr(f 2 ) value (the final wr(f 2 ) values were.685 (I > 2σ(I)) and.77 (all data)). The final Flack parameter (i.e. inversion twin population) is not zero (.124(5).) and indicates a small enantiomeric M contamination, as an enantiomorphous crystal phase. However, since the crystal is disordered, the standard uncertainty on this Flack parameter is certainly larger than the value obtained. S-14

Bipyridine 4a ORTEP plot of 4a. Thermal ellipsoids set at 5% probability and hydrogen atoms shown as sticks. Bipyridine 5b ORTEP plot of 5b (2 nd eluted peak). The axial configuration is P. Thermal ellipsoids set at 5% probability and hydrogen atoms shown as sticks. S-15

Details on the theoretical calculations All calculations were performed using the Gaussian9 Rev. B.1 program package (Frisch et al., 21). Energy barriers of racemisation Molecular structures of bipyridines and their relative transitions states of racemisation were optimized at the DFT level of theory using the B97D functional including dispersion correction. The basis set employed was cc-pvdz on all elements, and effective core potentials were used to model atomic cores of Bromine and Iodine atoms (Peterson et al., 23; Schuchardt et al., 27). Solvent effects (methanol) were taken into account through the polarisable continuum model. Vibration frequencies were computed for the ground states and the transition states (ultra fine grids were used). In the later case, it was checked that the imaginary frequencies transform the transition states structures toward the P and M enantiomers. Results are summarized in the Table below: Compound G TS1 a ν b G TS2 a ν b T c r 3 57.35-15 56.43-7 536 4a 46.92-27 46.65-16 399 4b 46.65-24 46.79-8 42 4c 48.22-27 47.5-4 383 4d 47.34-24 47.2-1 413 4e 49.62-26 5.55-13 444 5a 47.4-28 46.3-4 426 a Standard free energy of activation (T=298.15K), in Kcal.mol -1. b Imaginary vibration frequencies computed at the TS geometry, displayed as negative number in cm -1 c Racemisation temperature (T r, in C) as solution of the non-linear equation: ln(2)/t r =(k B.T r /h).exp(- G /(R.T r )), where k B is the Boltzmann constant, h the Planck constant and R the ideal gas constant. Optimized molecular structures of ground (M enantiomers) and transition states TS1 & TS2 (color scheme: grey: carbon, blue: nitrogen, white: hydrogen, brown: bromine, magenta: iodine, red: oxygen, green: chlorine) 3 ground state M-enantiomer, TS1, TS2: S-16

4a ground state M-enantiomer, TS1, TS2: 4b ground state M-enantiomer, TS1, TS2: S-17

4c ground state M-enantiomer, TS1, TS2: 4d ground state M-enantiomer, TS1, TS2: S-18

4e ground state M-enantiomer, TS1, TS2: 5a ground state M-enantiomer, TS1, TS2: S-19

Atomic coordinates and absolute energies (T=298.15K) of 3: ground state C -.88411 2.898981 -.463578 C -.84695 1.493373 -.494612 C -.1727.745447.353399 C.84695 1.488237 1.2232 C.823116 2.892829 1.1719.1755 3.583932.353918 H -1.4613 3.487355-1.12827 H 1.483316 3.471159 1.83443 C.1727 -.745447.353399 C -.84695-1.488237 1.2232 C.84695-1.493373 -.494612 C -.823116-2.892829 1.1719 C.88411-2.898981 -.463578 -.1755-3.583932.353918 H -1.483316-3.471159 1.83443 H 1.4613-3.487355-1.12827 Br 2.51599.59969 2.49371 Br -2.51599 -.59969 2.49371 I -2.19643.52592-1.85157 I 2.19643 -.52592-1.85157 Zero-point correction=.111611 (Hartree/Particle) Thermal correction to Energy=.127288 Thermal correction to Enthalpy=.128233 Thermal correction to Gibbs Free Energy=.6335 Sum of electronic and zero-point Energies= -192.44781 Sum of electronic and thermal Energies= -192.432132 Sum of electronic and thermal Enthalpies= -192.431188 Sum of electronic and thermal Free Energies= -192.4967 Atomic coordinates and absolute energies (T=298.15K) of 3: Transition State 1 C 2.59485-1.56468 -.633537 C 1.517142 -.67482 -.86171 C.71565 -.23417.243385 C 1.47637 -.276345 1.464534 C 2.57694-1.137941 1.63396 3.4999-1.881883.58716 H 3.121736-1.996-1.49112 H 3.9467-1.211521 2.566832 C -.71565.23417.243385 C -1.47637.276345 1.464534 C -1.517142.67482 -.86171 C -2.57694 1.137941 1.63396 C -2.59485 1.56468 -.633537-3.4999 1.881883.58716 H -3.9467 1.211521 2.566832 H -3.121736 1.996-1.49112 Br 1.324718 1.7162 2.857796 Br -1.324718-1.7162 2.857796 I 1.739272.363889-2.74483 I -1.739272 -.363889-2.74483 S-2

Zero-point correction=.1969 (Hartree/Particle) Thermal correction to Energy=.124433 Thermal correction to Enthalpy=.125377 Thermal correction to Gibbs Free Energy=.64713 Sum of electronic and zero-point Energies= -192.35972 Sum of electronic and thermal Energies= -192.344959 Sum of electronic and thermal Enthalpies= -192.34414 Sum of electronic and thermal Free Energies= -192.44679 Atomic coordinates and absolute energies (T=298.15K) of 3: Transition State 2 C -1.433458.79543-2.761588 C -1.348732.274479-1.428967 C -.82911.296819 -.7351 C.994316.181424-1.684532 C.82996.624293-3.7567 -.356127 1.6469-3.51485 H -2.413366.787875-3.249739 H 1.6914.634884-3.68654 C.8291.35888.7351 C -.994318.473485 1.684532 C 1.348731.38427 1.428968 C -.82999.3616 3.7567 C 1.433455 -.54638 2.761589.356124 -.351562 3.51485 H -1.69143.226 3.68653 H 2.413363 -.13297 3.249741 Br 2.544652 -.945134-1.414829 Br -2.544652 1.644 1.414827 I -3.29389 -.965981 -.84698 I 3.29389 1.62886.8471 Zero-point correction=.19738 (Hartree/Particle) Thermal correction to Energy=.124459 Thermal correction to Enthalpy=.12543 Thermal correction to Gibbs Free Energy=.64197 Sum of electronic and zero-point Energies= -192.36597 Sum of electronic and thermal Energies= -192.345876 Sum of electronic and thermal Enthalpies= -192.344932 Sum of electronic and thermal Free Energies= -192.46138 Atomic coordinates and absolute energies (T=298.15K) of 4a: ground state Br 1.89726 -.358397-2.73919 1.85612 3.74821 -.41713 C -.466996 1.65247 2.97455 H.56662 1.943949 3.189468 C 1.377487.93615-1.43756 C.96195 2.82759.5117 H.72989 3.573291 1.272893 C.37693.64847 -.46177 C.13132 1.622548.544497 C -.858189 1.424277 1.635634 C -1.377487 1.459597 4.25227 H -1.5462 1.624587 5.59992 C -2.183993 1.14861 1.36955 H -2.55422.858996.334876 S-21

C -2.692247 1.4216 3.75232 H -3.42782.887543 4.573216 C 2.89544 2.14552-1.345666 H 2.876562 2.359412-2.8486 C -3.93419.824661 2.42128 H -4.1263.59596 2.199355 Br -1.89726.358397-2.73919-1.85612-3.74821 -.41713 C.466996-1.65247 2.97455 H -.56662-1.943949 3.189468 C -1.377487 -.93615-1.43756 C -.96195-2.82759.5117 H -.72989-3.573291 1.272893 C -.37693 -.64847 -.46177 C -.13132-1.622548.544497 C.858189-1.424277 1.635634 C 1.377487-1.459597 4.25227 H 1.5462-1.624587 5.59992 C 2.183993-1.14861 1.36955 H 2.55422 -.858996.334876 C 2.692247-1.4216 3.75232 H 3.42782 -.887543 4.573216 C -2.89544-2.14552-1.345666 H -2.876562-2.359412-2.8486 C 3.93419 -.824661 2.42128 H 4.1263 -.59596 2.199355 Zero-point correction=.29374 (Hartree/Particle) Thermal correction to Energy=.312121 Thermal correction to Enthalpy=.31366 Thermal correction to Gibbs Free Energy=.237598 Sum of electronic and zero-point Energies= -179.853945 Sum of electronic and thermal Energies= -179.832198 Sum of electronic and thermal Enthalpies= -179.831254 Sum of electronic and thermal Free Energies= -179.96721 Atomic coordinates and absolute energies (T=298.15K) of 4a: Transition State 1 Br -.46273 1.545745-3.58647 1.155161 3.427 -.374144 C -.641554 1.388174 2.985634 H.33177 1.827929 3.225613 C.323258 1.638791-1.82669 C.537616 2.749457.626941 H.482469 3.28436 1.58598 C.68938.743639 -.725521 C -.61631 1.47926.52315 C -.949879 1.6871 1.642481 C -1.544688 1.96713 4.18176 H -1.278813 1.341285 5.53315 C -2.191521.44859 1.36475 H -2.453777.21138.327832 C -2.769123.469199 3.731498 H -3.472465.234272 4.539287 C.952663 2.88139-1.593488 H 1.269547 3.483393-2.454966 C -3.88263.146491 2.398368 H -4.46326 -.331397 2.161276 Br.46396-1.545591-3.58658-1.155121-3.4219 -.374284 S-22

C.64157-1.388232 2.98566 H -.331822-1.827996 3.225545 C -.323181-1.638694-1.8273 C -.53762-2.749438.626838 H -.482481-3.28448 1.585789 C -.68889 -.743576 -.725547 C.61648-1.479184.52314 C.949867-1.68725 1.64247 C 1.544616-1.9686 4.1818 H 1.278713-1.341412 5.5334 C 2.191516 -.44864 1.364747 H 2.453799 -.21128.327889 C 2.76958 -.469283 3.731554 H 3.47238 -.234383 4.539369 C -.952591-2.8849-1.59366 H -1.269453-3.483275-2.455111 C 3.88232 -.146531 2.398443 H 4.4631.331365 2.161391 Zero-point correction=.289193 (Hartree/Particle) Thermal correction to Energy=.39784 Thermal correction to Enthalpy=.31728 Thermal correction to Gibbs Free Energy=.23928 Sum of electronic and zero-point Energies= -179.78196 Sum of electronic and thermal Energies= -179.76137 Sum of electronic and thermal Enthalpies= -179.76426 Sum of electronic and thermal Free Energies= -179.831946 Atomic coordinates and absolute energies (T=298.15K) of 4a: Transition State 2 Br 2.2154.975755 3.28654.616137 3.482785.482455 C -2.872388.735793 2.19498 H -2.129229.33513 2.84554 C 1.179481 1.477129 1.7158 C -.66829 2.946258.341768 H -1.377325 3.66443 -.78279 C.5793.73977 1.195292 C -.984885 1.645324.745814 C -2.43766 1.49519.942486 C -4.23965.598685 2.388921 H -4.55517.75172 3.299197 C -3.413993 1.963645.78375 H -3.9865 2.466949 -.841895 C -5.228 1.143443 1.516989 H -6.268783 1.36632 1.737416 C 1.4534 2.779189 1.26827 H 2.379167 3.276568 1.586152 C -4.779878 1.832248.36435 H -5.5251 2.258371 -.323288 Br -2.2154 -.975755 -.917785 -.616136-3.482785 1.88413 C 3.413993-1.963645 2.284494 H 3.9865-2.466949 3.24763 C -1.179481-1.477129.64769 C.66829-2.946258 2.2111 H 1.377326-3.66443 2.441148 C -.5793 -.73977 1.167576 C.984885-1.645324 1.61755 C 2.43766-1.49519 1.42382 S-23

C 4.779878-1.832248 1.998519 H 5.5252-2.258371 2.686156 C 2.872388 -.735793.253371 H 2.129229 -.33513 -.441686 C 5.228-1.143443.845879 H 6.268784-1.36632.625453 C -1.4534-2.779189 1.94599 H -2.379167-3.276568.776717 C 4.23965 -.598685 -.2652 H 4.55517 -.75172 -.936328 Zero-point correction=.288881 (Hartree/Particle) Thermal correction to Energy=.39487 Thermal correction to Enthalpy=.31431 Thermal correction to Gibbs Free Energy=.23986 Sum of electronic and zero-point Energies= -179.782586 Sum of electronic and thermal Energies= -179.76198 Sum of electronic and thermal Enthalpies= -179.76136 Sum of electronic and thermal Free Energies= -179.832382 Atomic coordinates and absolute energies (T=298.15K) of 4b: ground state Br 1.915693 -.133767-3.463114 1.481394 3.273369-1.12932 C -.582133 1.59718 2.28768 H.396438 2.53279 2.466988 C 1.24921 1.9268-2.125965 C.582133 2.889831 -.26487 H.324477 3.634371.559253 C.29237.687431-1.17427 C -.46743 1.624868 -.15995 C -.966789 1.31299.956551 C -1.398252 1.271172 3.373622 H -1.51678 1.49529 4.386126 C -2.22868.677828.748991 H -2.557453.458419 -.26897 C -2.63791.633273 3.15123 C 1.81479 2.377593-2.76174 H 2.561735 2.68274-2.81985 C -3.45728.348793 1.82574 H -4.1856 -.13354 1.664932 Br -1.915693.133767-3.463114-1.481394-3.273369-1.12932 C.582133-1.59718 2.28768 H -.396438-2.53279 2.466988 C -1.24921-1.9268-2.125965 C -.582133-2.889831 -.26487 H -.324477-3.634371.559253 C -.29237 -.687431-1.17427 C.46743-1.624868 -.15995 C.966789-1.31299.956551 C 1.398252-1.271172 3.373622 H 1.51678-1.49529 4.386126 C 2.22868 -.677828.748991 H 2.557453 -.458419 -.26897 C 2.63791 -.633273 3.15123 C -1.81479-2.377593-2.76174 H -2.561735-2.68274-2.81985 C 3.45728 -.348793 1.82574 S-24

H 4.1856.13354 1.664932 O 3.5834 -.253545 4.13241 O -3.5834.253545 4.13241 C -3.122589.5249 5.494295 H -3.948587.116848 6.113739 H -2.18211 -.29637 5.743819 H -2.987116 1.587557 5.677827 C 3.122589 -.5249 5.494295 H 3.948587 -.116848 6.113739 H 2.18211.29637 5.743819 H 2.987116-1.587557 5.677827 Zero-point correction=.35284 (Hartree/Particle) Thermal correction to Energy=.37991 Thermal correction to Enthalpy=.38854 Thermal correction to Gibbs Free Energy=.292849 Sum of electronic and zero-point Energies= -219.717694 Sum of electronic and thermal Energies= -219.69588 Sum of electronic and thermal Enthalpies= -219.689643 Sum of electronic and thermal Free Energies= -219.777648 Atomic coordinates and absolute energies (T=298.15K) of 4b: Transition State 1 Br -.3371 1.584968-3.775324 1.381667 3.317322 -.544364 C -.55867 1.417362 2.823 H.431624 1.81547 3.4581 C.438416 1.617949-1.998785 C.714832 2.78379.45893 H.696386 3.237872 1.41245 C.113296.739962 -.9631 C.2196 1.48538.34174 C -.879714 1.12173 1.458995 C -1.452399 1.158162 3.85293 H -1.151632 1.384835 4.876673 C -2.151395.5537 1.19679 H -2.43784.326898.162838 C -2.76452.574673 3.569612 C 1.147643 2.812577-1.76739 H 1.53766 3.398249-2.625628 C -3.4863.27693 2.22731 H -4.32386 -.156745 2.17699 Br.31571-1.58185-3.777448-1.386127-3.31321 -.534774 C.577955-1.413992 2.798345 H -.4143-1.81228 3.48747 C -.452749-1.613965-1.995679 C -.712389-2.74321.455853 H -.6874-3.233818 1.417258 C -.1271 -.73598 -.95477 C -.2134-1.481327.341927 C.889346-1.117841 1.452873 C 1.47898-1.154732 3.8459 H 1.185634-1.381833 4.868491 C 2.158968 -.5461 1.181137 H 2.43874 -.322196.145969 C 2.73737 -.57574 3.55685 C -1.1646-2.88527-1.75941 H -1.522498-3.39429-2.615153 S-25

C 3.62774 -.272434 2.25796 H 4.45417.161686 1.989613 O -3.651347.264433 4.52937 O 3.68199 -.2638 4.477422 C 3.382493 -.536513 5.856235 H 4.269169 -.212753 6.42492 H 2.49325.31637 6.189154 H 3.25455-1.619498 6.14365 C -3.342157.5463 5.879663 H -4.22515.217528 6.45443 H -2.44817 -.28232 6.26427 H -3.16329 1.623472 6.3665 Zero-point correction=.35172 (Hartree/Particle) Thermal correction to Energy=.37766 Thermal correction to Enthalpy=.37865 Thermal correction to Gibbs Free Energy=.294915 Sum of electronic and zero-point Energies= -219.646514 Sum of electronic and thermal Energies= -219.62555 Sum of electronic and thermal Enthalpies= -219.619611 Sum of electronic and thermal Free Energies= -219.733 Atomic coordinates and absolute energies (T=298.15K) of 4b: Transition State 2 Br 2.419267.765857 3.123211.83929 3.44364.494916 C -2.73636.873278 2.345776 H -1.974161.389773 2.966324 C 1.317723 1.38243 1.6587 C -.459888 2.996444.44182 H -1.21277 3.714735.84176 C.18693.731838 1.2778 C -.9272 1.7265.867822 C -2.3492 1.574117 1.17653 C -4.73973.83157 2.728733 H -4.372655.269185 3.637826 C -3.34988 2.219673.42421 H -3.8361 2.746943 -.498269 C -5.73524 1.443216 1.9559 C 1.647454 2.6687 1.2948 H 2.622381 3.9946 1.47157 C -4.69841 2.16225.798424 H -5.447256 2.663497.17984 Br -2.41956 -.76565 -.761672 -.84222-3.442857 1.866623 C 3.349515-2.219466 1.937338 H 3.83317-2.746736 2.85988 C -1.31816-1.3836.71732 C.459595-2.996237 1.919737 H 1.29984-3.714528 2.277363 C -.18986 -.731631 1.153759 C.91779-1.72443 1.493717 C 2.339799-1.57391 1.18536 C 4.69818-2.16243 1.563115 H 5.446963-2.66329 2.182455 C 2.735743 -.87371.15763 H 1.973869 -.389566 -.64785 C 5.73231-1.4438.45639 C -1.647747-2.667863 1.152491 H -2.622674-3.99199.8932 S-26

C 4.7368 -.8295 -.367194 H 4.372362 -.268978-1.276287 O 6.34996-1.311476 -.52545 O -6.35199 1.311683 2.41484 C 7.397796-1.953627.694981 H 8.33134-1.725372.155329 H 7.449524-1.553649 1.727594 H 7.24116-3.5363.734476 C -7.39889 1.953835 1.666558 H -7.449817 1.553856.633945 H -8.331327 1.725579 2.2621 H -7.24139 3.557 1.62763 Zero-point correction=.351692 (Hartree/Particle) Thermal correction to Energy=.377599 Thermal correction to Enthalpy=.378543 Thermal correction to Gibbs Free Energy=.295317 Sum of electronic and zero-point Energies= -219.64679 Sum of electronic and thermal Energies= -219.6281 Sum of electronic and thermal Enthalpies= -219.619857 Sum of electronic and thermal Free Energies= -219.7383 Atomic coordinates and absolute energies (T=298.15K) of 4c: ground state Br 1.917982.233377-3.21959.79573 3.52594 -.89747 C -1.22129 1.329121 2.59465 C 1.22129 1.311214-1.876 C -.24373 2.954942.19617 H -.43683 3.63665.777593 C.154789.7377 -.921823 C -.38375 1.589791.7669 C -1.32111 1.93765 1.131465 C -1.912669.857493 3.49662 H -1.75956 1.32495 4.555178 C -2.471137.38641.7954 H -2.69933.22737 -.269213 C -3.6915.15976 3.124328 C 1.312877 2.68316-1.82932 H 1.992297 3.127511-2.568241 C -3.356175 -.87888 1.771735 H -4.261227 -.631816 1.479155 Br -1.917982 -.233377-3.21959 -.79573-3.52594 -.89747 C 1.22129-1.329121 2.59465 C -1.22129-1.311214-1.876 C.24373-2.954942.19617 H.43683-3.63665.777593 C -.154789 -.7377 -.921823 C.38375-1.589791.7669 C 1.32111-1.93765 1.131465 C 1.912669 -.857493 3.49662 H 1.75956-1.32495 4.555178 C 2.471137 -.38641.7954 H 2.69933 -.22737 -.269213 C 3.6915 -.15976 3.124328 C -1.312877-2.68316-1.82932 H -1.992297-3.127511-2.568241 C 3.356175.87888 1.771735 S-27

H 4.261227.631816 1.479155 H -3.7463 -.211472 3.9743 H 3.7463.211472 3.9743 O.13285 2.48 2.783916 O -.13285-2.48 2.783916 C.45182 2.266797 4.157551 H 1.412767 2.85623 4.139299 H -.328842 2.89417 4.633358 H.56634 1.321657 4.72399 C -.45182-2.266797 4.157551 H -1.412767-2.85623 4.139299 H.328842-2.89417 4.633358 H -.56634-1.321657 4.72399 Zero-point correction=.353285 (Hartree/Particle) Thermal correction to Energy=.38138 Thermal correction to Enthalpy=.38183 Thermal correction to Gibbs Free Energy=.295969 Sum of electronic and zero-point Energies= -219.717614 Sum of electronic and thermal Energies= -219.69761 Sum of electronic and thermal Enthalpies= -219.689816 Sum of electronic and thermal Free Energies= -219.77493 Atomic coordinates and absolute energies (T=298.15K) of 4c: Transition State 1 Br -.3326 1.572137-3.562893 1.122615 3.421252 -.294 C -.7949 1.34484 3.47341 C.374985 1.639486-1.757316 C.479694 2.76485.692255 H.391199 3.296618 1.643862 C.7625.746732 -.671483 C -.87339 1.479612.577252 C -1.15869 1.4492 1.659386 C -1.8349 1.23663 3.99861 H -1.632628 1.232212 5.5481 C -2.255731.47595 1.289192 H -2.442945.28921.226216 C -3.17546.456246 3.5856 H -3.785255.24617 4.337719 C.986363 2.88519-1.51111 H 1.337941 3.48526-2.361416 C -3.2482.172389 2.229836 H -4.199668 -.261147 1.92 Br.327889-1.5753-3.563618-1.124276-3.4259 -.29161 C.791416-1.34854 3.46339 C -.37776-1.638393-1.757518 C -.4859-2.764488.691798 H -.391369-3.296539 1.643179 C -.77954 -.745967 -.671648 C.86367-1.479222.576741 C 1.15734-1.44852 1.658291 C 1.8218-1.24373 3.989165 H 1.635118-1.233265 5.48847 C 2.255324 -.475773 1.287316 H 2.441715 -.288748.224253 C 3.18919 -.456867 3.582545 H 3.787221 -.24158 4.33473 S-28

C -.98896-2.883994-1.51123 H -1.3412-3.483743-2.361426 C 3.248529 -.172581 2.227288 H 4.199755.26132 1.898853 O.432844 1.83641 3.3924 O -.431676-1.8462 3.389989 C.693547 2.8781 4.77818 H.616899 1.168974 5.384142 H 1.727363 2.467221 4.8223 H -.7871 2.853632 5.15868 C -.691296-2.88736 4.7771 H -.614131-1.17147 5.384318 H -1.72599-2.468133 4.82787 H.144-2.854737 5.157644 Zero-point correction=.35218 (Hartree/Particle) Thermal correction to Energy=.377772 Thermal correction to Enthalpy=.378716 Thermal correction to Gibbs Free Energy=.297114 Sum of electronic and zero-point Energies= -219.64386 Sum of electronic and thermal Energies= -219.617423 Sum of electronic and thermal Enthalpies= -219.616479 Sum of electronic and thermal Free Energies= -219.6988 Atomic coordinates and absolute energies (T=298.15K) of 4c: Transition State 2 Br 2.13341.746183 3.429839.625133 3.542476.87443 C -2.825114.69222 2.19118 H -2.46951.299823 2.855858 C 1.16397 1.414248 1.891239 C -.587636 3.22748.623948 H -1.33998 3.716535.2324 C.58614.73575 1.264451 C -.972551 1.684123.874795 C -2.423865 1.41116 1.4178 C -4.174999.486428 2.55814 H -4.44943 -.741 3.48743 C -3.445924 1.94312.192199 C -5.164428 1.23985 1.666217 H -6.226829.885345 1.89975 C 1.441453 2.757474 1.64291 H 2.349676 3.221319 2.1139 C -4.84483 1.749869.518967 H -5.587476 2.15378 -.13331 Br -2.13341 -.746183-1.6697 -.625132-3.542476 1.488825 C 3.445925-1.94312 2.17669 C -1.16396-1.414248.471629 C.587637-3.22748 1.73892 H 1.33998-3.716535 2.13468 C -.58614 -.73575 1.98418 C.972552-1.684123 1.48873 C 2.423865-1.41116 1.32188 C 4.84483-1.749869 1.84391 H 5.587476-2.15378 2.4932 C 2.825114 -.69222.171761 H 2.46951 -.299823 -.49299 C 5.164429-1.23985.696651 S-29

H 6.22683 -.885345.463163 C -1.441453-2.757474.758578 H -2.349676-3.221319.35156 C 4.174999 -.486428 -.142946 H 4.44943.741-1.45875 O 3.24962-2.568889 3.36584 O -3.24961 2.568889 -.943716 C 4.1849-3.64379 4.218985 H 4.656118-2.23852 4.59253 H 3.45469-3.5126 5.52729 H 4.654938-3.832266 3.736275 C -4.1849 3.64379-1.856117 H -3.45469 3.5126-2.68986 H -4.656117 2.23852-2.229185 H -4.654937 3.832266-1.37346 Zero-point correction=.351665 (Hartree/Particle) Thermal correction to Energy=.37767 Thermal correction to Enthalpy=.378551 Thermal correction to Gibbs Free Energy=.29565 Sum of electronic and zero-point Energies= -219.643935 Sum of electronic and thermal Energies= -219.617993 Sum of electronic and thermal Enthalpies= -219.61748 Sum of electronic and thermal Free Energies= -219.69995 Atomic coordinates and absolute energies (T=298.15K) of 4d: ground state Br 1.91779 -.134789-3.399489 1.46527 3.28774-1.81876 C -.57412 1.58939 2.337813 H.411826 2.36392 2.523618 C 1.248229 1.92145-2.68662 C.57412 2.896383 -.15545 H.38869 3.642457.67224 C.291676.687785-1.11571 C -.4824 1.627836 -.16394 C -.96791 1.32317 1.13279 C -1.39143 1.264221 3.426254 H -1.65665 1.47934 4.45238 C -2.22471.694494.79822 H -2.562426.48532 -.221185 C -2.627659.64586 3.182441 C 1.84237 2.381692-2.22823 H 2.55163 2.687439-2.766414 C -3.5759.361926 1.874671 H -4.384 -.1868 1.7248 Br -1.91779.134789-3.399489-1.46527-3.28774-1.81876 C.57412-1.58939 2.337813 H -.411826-2.36392 2.523618 C -1.248229-1.92145-2.68662 C -.57412-2.896383 -.15545 H -.38869-3.642457.67224 C -.291676 -.687785-1.11571 C.4824-1.627836 -.16394 C.96791-1.32317 1.13279 C 1.39143-1.264221 3.426254 H 1.65665-1.47934 4.45238 C 2.22471 -.694494.79822 H 2.562426 -.48532 -.221185 S-3

C 2.627659 -.64586 3.182441 C -1.84237-2.381692-2.22823 H -2.55163-2.687439-2.766414 C 3.5759 -.361926 1.874671 H 4.384.1868 1.7248 Cl -3.661165.28581 4.545915 Cl 3.661165 -.28581 4.545915 Zero-point correction=.271488 (Hartree/Particle) Thermal correction to Energy=.295785 Thermal correction to Enthalpy=.296729 Thermal correction to Gibbs Free Energy=.214194 Sum of electronic and zero-point Energies= -271.133573 Sum of electronic and thermal Energies= -271.19277 Sum of electronic and thermal Enthalpies= -271.18333 Sum of electronic and thermal Free Energies= -271.19867 Atomic coordinates and absolute energies (T=298.15K) of 4d: Transition State 1 Br -.39858 1.56798-3.93615 1.244857 3.37958 -.714929 C -.62693 1.41931 2.638533 H.374463 1.83227 2.881917 C.3733 1.629863-2.16675 C.63957 2.736612.282943 H.555724 3.271769 1.239861 C.88599.741955-1.72348 C -.25299 1.481494.1761 C -.919199 1.89748 1.296188 C -1.495675 1.12337 3.68137 H -1.228383 1.355139 4.71671 C -2.171119.488199 1.26774 H -2.448959.25527 -.6299 C -2.722212.51316 3.381697 C 1.37135 2.852827-1.934374 H 1.378991 3.444721-2.794143 C -3.7691.19864 2.57154 H -4.3686 -.272532 1.83425 Br.39858-1.56798-3.93615-1.244857-3.37958 -.714929 C.62693-1.41931 2.638533 H -.374463-1.83227 2.881917 C -.3733-1.629863-2.16675 C -.63957-2.736612.282943 H -.555724-3.271769 1.239861 C -.88599 -.741955-1.72348 C.25299-1.481494.1761 C.919199-1.89748 1.296188 C 1.495675-1.12337 3.68137 H 1.228383-1.355139 4.71671 C 2.171119 -.488199 1.26774 H 2.448959 -.25527 -.6299 C 2.722212 -.51316 3.381697 C -1.37135-2.852827-1.934374 H -1.378991-3.444721-2.794143 C 3.7691 -.19864 2.57154 H 4.3686.272532 1.83425 Cl -3.846834.132963 4.688269 Cl 3.846834 -.132963 4.688269 S-31

Zero-point correction=.27382 (Hartree/Particle) Thermal correction to Energy=.293535 Thermal correction to Enthalpy=.294479 Thermal correction to Gibbs Free Energy=.216772 Sum of electronic and zero-point Energies= -271.6181 Sum of electronic and thermal Energies= -271.38657 Sum of electronic and thermal Enthalpies= -271.37713 Sum of electronic and thermal Free Energies= -271.115419 Atomic coordinates and absolute energies (T=298.15K) of 4d: Transition State 2 Br 2.144737 1.774761 1.568642.7853 3.2943-1.64581 C -2.896585.59528.943538 H -2.74818.4916 1.659196 C.983122 1.7931.23486 C -1.6134 2.58717-1.52894 H -1.93785 2.93242-2.38743 C -.4672.71692 -.18576 C -1.228219 1.33122 -.766713 C -2.618464.97738 -.39528 C -4.2842.361878 1.37359 H -4.49223.69779 2.4933 C -3.77657 1.147524-1.27969 H -3.52853 1.4231-2.323491 C -5.265614.52596.461967 C 1.4587 2.855161 -.773556 H 1.96645 3.53221 -.686 C -5.25963.92656 -.863624 H -5.85722 1.477-1.56527 Br -2.144737-1.774761-1.568642 -.7853-3.2943 1.64581 C 3.77657-1.147524 1.27969 H 3.52853-1.4231 2.323491 C -.983122-1.7931 -.23486 C 1.6134-2.58717 1.52894 H 1.93785-2.93242 2.38743 C.4672 -.71692.18576 C 1.228219-1.33122.766713 C 2.618464 -.97738.39528 C 5.25963 -.92656.863624 H 5.85722-1.477 1.56527 C 2.896585 -.59528 -.943538 H 2.74818 -.4916-1.659196 C 5.265614 -.52596 -.461967 C -1.4587-2.855161.773556 H -1.96645-3.53221.686 C 4.2842 -.361878-1.37359 H 4.49223 -.69779-2.4933 Cl -6.92189.232873.993458 Cl 6.92189 -.232873 -.993458 Zero-point correction=.27311 (Hartree/Particle) Thermal correction to Energy=.293422 Thermal correction to Enthalpy=.294366 Thermal correction to Gibbs Free Energy=.216423 Sum of electronic and zero-point Energies= -271.61765 Sum of electronic and thermal Energies= -271.38654 S-32

Sum of electronic and thermal Enthalpies= -271.3771 Sum of electronic and thermal Free Energies= -271.115653 Atomic coordinates and absolute energies (T=298.15K) of 4e: ground state Br -.797134 1.766616-3.65433-3.57326 -.372357-1.375131 C -1.553669.567921-2.294518 C -2.8998 -.97441 -.446399 H -3.336864-1.59314.289173 C -.74374 -.7482-1.336171 C -1.44288 -.858467 -.35688 C -2.947442.399262-2.28843 H -3.572424.97936-3.26793 Br.797134-1.766616-3.65433 3.57326.372357-1.375131 C 1.553669 -.567921-2.294518 C 2.8998.97441 -.446399 H 3.336864 1.59314.289173 C.74374.7482-1.336171 C 1.44288.858467 -.35688 C 2.947442 -.399262-2.28843 H 3.572424 -.97936-3.26793 C.67231 1.566961.728176 C 1.15239 1.346759 2.1183 C -.33457 2.485.4374 C 1.96191.365155 2.535391 C.336643 2.12491 3.123958 C -1.8673 3.22855 1.42781 H -.576327 2.645784 -.653867 C 2.257561.19777 3.87969 H 2.43432 -.281527 1.79644 C.6723 1.925797 4.496623 C -.67231 3.5514 2.737978 H -1.787442 3.935232 1.11653 C 1.618815.985124 4.87321 H 2.976589 -.58633 4.17928 H.1513 2.52441 5.253532 H -1.181949 3.632262 3.519738 H 1.86719.835954 5.929372 C -.67231-1.566961.728176 C -1.15239-1.346759 2.1183 C.33457-2.485.4374 C -1.96191 -.365155 2.535391 C -.336643-2.12491 3.123958 C 1.8673-3.22855 1.42781 H.576327-2.645784 -.653867 C -2.257561 -.19777 3.87969 H -2.43432.281527 1.79644 C -.6723-1.925797 4.496623 C.67231-3.5514 2.737978 H 1.787442-3.935232 1.11653 C -1.618815 -.985124 4.87321 H -2.976589.58633 4.17928 H -.1513-2.52441 5.253532 H 1.181949-3.632262 3.519738 H -1.86719 -.835954 5.929372 Zero-point correction=.38249 (Hartree/Particle) S-33

Thermal correction to Energy=.4962 Thermal correction to Enthalpy=.417 Thermal correction to Gibbs Free Energy=.323638 Sum of electronic and zero-point Energies= -297.835186 Sum of electronic and thermal Energies= -297.88172 Sum of electronic and thermal Enthalpies= -297.87228 Sum of electronic and thermal Free Energies= -297.893597 Atomic coordinates and absolute energies (T=298.15K) of 4e: Transition State 1 Br -1.12191 1.146315-3.549173 -.821322 3.5112 -.36142 C -.532847 1.58857-1.759563 C -1.3884 2.619328.679539 H -1.426432 3.29338 1.615469 C -.314233.68394 -.669342 C -.82536 1.229788.58143 C -.65122 2.974959-1.519715 H -.653856 3.664553-2.3752 Br 1.12174-1.143946-3.549525.821567-3.599 -.37517 C.53326-1.586437-1.76166 C 1.3122-2.618729.67856 H 1.426464-3.29131 1.614362 C.314526 -.67923 -.669591 C.825515-1.229146.579721 C.651584-2.97344-1.52885 H.654333-3.662676-2.376478 C -1.422625.393735 1.662139 C -1.37671.76248 3.58428 C -2.23258 -.6813 1.27411 C -.467879 1.735566 3.579972 C -2.226343.62985 3.99395 C -3.28836-1.39234 2.24945 H -2.28892 -.953166.21418 C -.45814 2.5275 4.929283 H.255888 2.22513 2.964 C -2.256.429775 5.373972 C -3.4756-1.8283 3.5394 H -3.654677-2.219615 1.854943 C -1.33951 1.41932 5.835786 H.2719 2.788796 5.3271 H -2.864791 -.1251 6.66377 H -3.683826-1.53255 4.264141 H -1.319931 1.674767 6.89993 C 1.42267 -.393543 1.662126 C 1.37575 -.76633 3.58259 C 2.232664.681652 1.274525 C.467731-1.736165 3.579313 C 2.226151 -.63753 3.99419 C 3.28824 1.3924 2.2583 H 2.28182.953955.214738 C.45533-2.5386 4.928492 H -.255972-2.22834 2.9548 C 2.2229 -.43119 5.37423 C 3.4699 1.773 3.53977 H 3.6547 2.21973 1.856234 C 1.338678-1.412458 5.835348 H -.27148-2.7914 5.395 H 2.86439.1894 6.66713 S-34

H 3.68363 1.529377 4.265151 H 1.319451-1.67673 6.899354 Zero-point correction=.38912 (Hartree/Particle) Thermal correction to Energy=.46765 Thermal correction to Enthalpy=.4779 Thermal correction to Gibbs Free Energy=.325451 Sum of electronic and zero-point Energies= -297.75969 Sum of electronic and thermal Energies= -297.733216 Sum of electronic and thermal Enthalpies= -297.732272 Sum of electronic and thermal Free Energies= -297.814529 Atomic coordinates and absolute energies (T=298.15K) of 4e: Transition State 2 Br 1.754417 1.8523 1.96389.269761 3.2898-1.517883 C.97367 1.726872.225221 C -.83958 2.537286-1.649741 H -1.62759 2.965424-2.279981 C -.2964.71892 -.1951 C -1.93115 1.39523 -.994667 C 1.77658 2.911214 -.51712 H 1.886586 3.62448 -.23895 Br -1.754417-1.8523-1.96389 -.269761-3.2898 1.517883 C -.97367-1.726872 -.225221 C.83958-2.537286 1.649741 H 1.62759-2.965424 2.279981 C.2964 -.71892.1951 C 1.93115-1.39523.994667 C -1.77658-2.911214.51712 H -1.886586-3.62448.23895 C 2.52513 -.914511.888461 C 3.457649 -.971988 1.993588 C 3.11648 -.646718 -.396978 C 3.5852-1.119434 3.35467 C 4.867374 -.795549 1.723855 C 4.39141 -.447732 -.645721 H 2.36857 -.622231-1.23517 C 3.979486-1.153231 4.386195 H 1.982785-1.178725 3.585199 C 5.79914 -.849946 2.85877 C 5.36857 -.535733.39233 H 4.729144 -.248678-1.66949 C 5.3755-1.33824 4.11196 H 3.636335-1.261949 5.42291 H 6.86616 -.727787 2.58626 H 6.3873 -.42769.27588 H 6.95591-1.69123 4.932531 C -2.52513.914511 -.888461 C -3.457649.971988-1.993588 C -3.11648.646718.396978 C -3.5852 1.119434-3.35467 C -4.867374.795549-1.723855 C -4.39141.447732.645721 H -2.36857.622231 1.23517 C -3.979486 1.153231-4.386195 H -1.982785 1.178725-3.585199 C -5.79914.849946-2.85877 C -5.36857.535733 -.39233 S-35

H -4.729144.248678 1.66949 C -5.3755 1.33824-4.11196 H -3.636335 1.261949-5.42291 H -6.86616.727787-2.58626 H -6.3873.42769 -.27588 H -6.95591 1.69123-4.932531 Zero-point correction=.3865 (Hartree/Particle) Thermal correction to Energy=.46598 Thermal correction to Enthalpy=.47542 Thermal correction to Gibbs Free Energy=.324761 Sum of electronic and zero-point Energies= -297.757147 Sum of electronic and thermal Energies= -297.7312 Sum of electronic and thermal Enthalpies= -297.73256 Sum of electronic and thermal Free Energies= -297.81337 Atomic coordinates and absolute energies (T=298.15K) of 5a: ground state Br -2.167749-2.926834 -.378219-1.691894 -.7717 3.15493 C -1.469549-1.78371.9499 C -.69142 -.1617 2.97694 H -.281213.659355 3.78725 C -.34199 -.923889.661282 C.1116 -.4181 1.686212 C -2.113524-1.6793 2.187891 H -2.998617-2.219948 2.43585 Br 2.187569-2.91815.35795 1.7422 -.716219-3.146852 C 1.483464-1.68661 -.945763 C.615593.26528-2.891658 H.28476.71788-3.683972 C.35188 -.91346 -.658368 C -.17269 -.2519-1.672326 C 2.129256-1.564769-2.19667 H 3.18932-2.167739-2.412849 C 1.24298.784843 1.45118 C -1.245879.794135-1.43546 C 2.228252 1.452294 1.137182 C -2.237365 1.453116-1.11818 C 3.368636 2.196752.71814 C 4.464 3.122628 1.587796 C 3.881364 2.959 -.595389 C 5.1257 3.84167 1.149755 H 3.69216 3.266822 2.599528 C 5.2574 2.734658-1.288 H 3.39673 1.29643-1.266575 C 5.627347 3.6565 -.151756 H 5.61287 4.55383 1.826863 H 5.391949 2.585231-2.347 H 6.54442 4.21539 -.48942 C -3.385325 2.188881 -.74111 C -4.18489 3.11499-1.575367 C -3.98299 1.99336.63987 C -5.147226 3.825279-1.14416 H -3.615823 3.265851-2.58338 C -5.37236 2.71261 1.2258 H -3.4194 1.279812 1.276532 C -5.659656 3.62645.152269 S-36

H -5.6353 4.538246-1.822285 H -5.434467 2.554215 2.31923 H -6.54279 4.184835.484326 Zero-point correction=.3915 (Hartree/Particle) Thermal correction to Energy=.335435 Thermal correction to Enthalpy=.336379 Thermal correction to Gibbs Free Energy=.242972 Sum of electronic and zero-point Energies= -1943.37758 Sum of electronic and thermal Energies= -1943.11338 Sum of electronic and thermal Enthalpies= -1943.1394 Sum of electronic and thermal Free Energies= -1943.1382 Atomic coordinates and absolute energies (T=298.15K) of 5a: Transition State 1 C 1.154-2.931944 -.21118 C.138942-1.84134.16624 C.66182 -.54398.127356 C 2.6276 -.546143.55426 C 2.832277-1.715191.3377 2.343946-2.86534 -.149868 H.565522-3.917652 -.4248 C.14874.816346 -.93524 C -1.372911 1.18498 -.178638 C.86357 1.994435 -.29557 C -1.783295 2.5617.94331 C.336444 3.289341 -.42761 -.943316 3.544553.255938 Br -1.628136-2.434146.523228 C 2.69198.474448 1.39622 C 3.288951 1.283899 2.23 Br -2.78976.166876-1.9388 H -2.857377 2.727196.148629 H 3.92215-1.686541.575871 H 1.18269 4.147526 -.18716 C 2.163727 1.95247 -.845917 C 3.273823 2.6944-1.37827 C 3.92334 2.297284 2.79453 C 3.27451 3.47885 3.133269 C 5.275122 2.159115 3.28228 C 3.834223 4.489594 3.872667 H 2.16582 3.584943 2.81769 C 5.889838 3.179316 3.94635 H 5.82861 1.25118 2.943548 C 5.17438 4.34523 4.281177 H 3.275463 5.396641 4.131789 H 6.933276 3.65573 4.26382 H 5.66294 5.139869 4.8595 C 4.577635 1.97547-1.945345 C 5.321581 3.17185-2.133178 C 5.16517.729943-2.311752 C 6.614554 3.11842-2.67576 H 4.874477 4.13174-1.849757 C 6.453791.691114-2.84966 H 4.587564 -.192619-2.166635 C 7.184547 1.881464-3.3152 H 7.182195 4.45551-2.81316 H 6.89587 -.272721-3.127894 H 8.19637 1.845443-3.45788 S-37

Zero-point correction=.37543 (Hartree/Particle) Thermal correction to Energy=.332855 Thermal correction to Enthalpy=.333799 Thermal correction to Gibbs Free Energy=.246712 Sum of electronic and zero-point Energies= -1942.96811 Sum of electronic and thermal Energies= -1942.942699 Sum of electronic and thermal Enthalpies= -1942.941755 Sum of electronic and thermal Free Energies= -1943.28841 Atomic coordinates and absolute energies (T=298.15K) of 5a: Transition State 2 C -2.191575-2.18229 -.7913 C -1.733918 -.898952 -.241796 C -.3236 -.65859 -.5995 C.391539-1.92867.76326 C -.167598-3.94291 -.51728-1.396366-3.173358-1.25343 H -3.259491-2.226982-1.15336 C.322775.655825.6256 C 1.73392.896718.24213 C -.392364 1.918633 -.762 C 2.19749 2.15995.7941 C.166773 3.9257.5234 1.39554 3.171124 1.25649 Br -3.14734.138916.584269 C 1.5587-2.1127.925478 C 2.366886-2.397655 1.76152 Br 3.146479 -.14115 -.583963 H 3.258666 2.224748 1.15642 H -.434923 4.1872.49355 H.43498-4.1316 -.492749 C -1.56695 2.17793 -.925172 C -2.367712 2.395421-1.761214 C 3.396321-2.627626 2.71442 C 3.921657-3.932512 2.92233 C 3.919389-1.53966 3.46796 C 4.943786-4.13687 3.85867 H 3.519884-4.77115 2.342781 C 4.94821-1.75875 4.4142 H 3.514916 -.534297 3.3686 C 5.455986-3.54596 4.618 H 5.343956-5.14591 4.12357 H 5.33886 -.91492 4.976822 H 6.25525-3.22594 5.331875 C -3.397147 2.625392-2.714114 C -3.922482 3.93278-2.921996 C -3.92215 1.537426-3.467653 C -4.944612 4.134636-3.85831 H -3.5279 4.768781-2.342475 C -4.941646 1.756516-4.4736 H -3.515741.53263-3.36554 C -5.456811 3.52362-4.599711 H -5.344782 5.143676-4.125 H -5.339685.912686-4.976516 H -6.25676 3.21836-5.331569 Zero-point correction=.37447 (Hartree/Particle) Thermal correction to Energy=.332743 Thermal correction to Enthalpy=.333688 S-38

Thermal correction to Gibbs Free Energy=.247291 Sum of electronic and zero-point Energies= -1942.97298 Sum of electronic and thermal Energies= -1942.9451 Sum of electronic and thermal Enthalpies= -1942.94457 Sum of electronic and thermal Free Energies= -1943.3453 S-39

Electronic circular dichroism calculations Molecular structures were first optimized at the DFT level of theory, using the CAM-B3LYP functional and the 6-311+G(d,p) basis set for all elements. Solvent effects (methanol) were taken into account through the polarisable continuum model. Rotational strengths were then calculated on the converged molecular structures at the TD-DFT level of theory, using the same functional and basis sets. In these calculations, solvent effects were taken into account in the non-equilibrium formalism. ECD spectra were finally obtained as superposition of Gaussian functions (half-height width set to.25ev) centred on the previously determined absorption wavelengths. Results are reported in Fig. 1 to 6, where data are given as ε in L.mol -1.cm -1. As can been seen in comparison to experimental data, theoretical ECD spectra are systematically shifted to shorter wavelengths, as noticed in previous studies (Pipolo et al., 211). References Peterson, K.A., Figgen, D., Goll, E., Stoll, H. and Dolg, M. J. Chem. Phys. 23, 119, 11113. Schuchardt, K.L., Didier, B.T., Elsethagen, T., Sun, L., Gurumoorthi, V., Chase, J., Li, J., and Windus, T.L. J. Chem. Inf. Model. 27, 47, 145. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. akatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. akajima, Y. Honda, O. Kitao, H. akai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K.. Kudin, V.. Staroverov, T. Keith, R. Kobayashi, J. ormand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi,. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 21. Pipolo, S., Percudani, R., Cammi, R. Org. Biomol. Chem. 211, 9, 5149. S-4

Fig. 1 Comparison of experimental (black triangles, 1 st peak in chiral HPLC) and theoretical (squares) ECD spectra of 4a-M enantiomer. Fig.2 Comparison of experimental (black triangles, 1 st peak in chiral HPLC) and theoretical (squares) ECD spectra of 4c-M enantiomer. Fig. 3 Comparison of experimental (black triangles, 2 nd peak in chiral HPLC) and theoretical (squares) ECD spectra of 4d-M enantiomer. S-41

Fig. 4 Comparison of experimental (black triangles, 1 st peak in chiral HPLC) and theoretical (squares) ECD spectra of 4e-M enantiomer. Fig. 5 Comparison of experimental (black triangles, 1 st peak in chiral HPLC) and theoretical (squares) ECD spectra of 4f-M enantiomer. Fig. 6 Comparison of experimental (black triangles, 1 st peak in chiral HPLC) and theoretical (squares) ECD spectra of 5a-M enantiomer. S-42