Keto-Enol Thermodynamics of Breslow Intermediates

Keto-Enol Thermodynamics of Breslow Intermediates Mathias Paul, Martin Breugst, Jörg-Martin Neudörfl, Raghavan B. Sunoj, and Albrecht Berkessel Computational Section of the Supporting Information 1 Computational Details... S2 2 Additional Hammett Correlations... S3 3 Graphical Representations of the Lowest-Energy Structures of the Breslow Intermediates... S4 4 Graphical Representations of the Lowest-Energy Structures of the Ketone Tautomers... S6 5 Solvent-Dependence of the Keto-Enol-Energy Difference... S8 6 Coordinates and Calculated Energies for Free Carbenes... S9 7 Coordinates and Calculated Energies for Free Aldehydes... S16 8 Coordinates and Calculated Energies for Breslow Intermediates... S21 9 Coordinates and Calculated Energies for Ketones... S45 10 References... S67 S1

1 Computational Details The conformational space of each structure was explored a modified Monte Carlo search routine implemented in MacroModel 10.2 1 with the OPLS-2005 force field 2 and. An energy cutoff of 20 kcal mol 1 was used during the conformational analysis and structures with a heavy atom root-mean-square deviation (RMSD) less than 1.5 Å after the initial force field optimization were considered to be the same conformer. All remaining structures were then optimized in the gas phase employing the local meta-gga functional M06-L 3 with Grimme s dispersion-correction D3 4 and the double-ζ split-valence basis set 6-31+G(d,p) as well as density fitting. In addition to the force field structures, we also included geometries obtained from previously determined crystal structures as additional starting points for the geometry optimization. Subsequent vibrational analysis verified that each structure was a minimum. Thermal corrections were calculated from unscaled harmonic vibrational frequencies at the same level of theory for a standard state of 1 mol L 1 and 298.15 K. The entropic contributions to the reported free energies were derived from partition functions evaluated using Truhlar s quasiharmonic correction. 5 This method uses the same approximations as the usual harmonic oscillator except that all vibrational frequencies lower than 100 cm 1 are set equal to 100 cm 1 to correct for the breakdown of the harmonic oscillator approximation for low frequencies. Electronic energies were subsequently obtained from single-point calculations of the M06-L geometries employing the meta-hybrid M06-2X functional, 6 Grimme s dispersion-correction D3 (zero damping), 4 the large triple-ζ def2-tzvpp basis set, 7 a level which is expected to result in accurate energies. 8 Solvation by tetrahydrofuran was taken into account by using the integral equation formalism polarizable continuum model (IEFPCM) 9 during the single point calculations. Throughout this investigation, an ultrafine grid corresponding to 99 radial shells and 590 angular points was used for the numerical integration of the density. 10 All density functional theory calculations were performed with Gaussian 09. 11 S2

2 Additional Hammett Correlations Dipp N OH N Dipp X G KE Dipp N O N Dipp X Dipp N + N Dipp H O X G Breslow Dipp N OH N Dipp X ΔΔG KE +6.0 +4.0 +2.0 0.0 2.0 4.0 1.0 ΔΔG KE = 5.09σ P + 1.13 r 2 = 0.94 X = NMe 2 0.5 X = H X = OMe σ p X = CN X = Br X = CF 3 0.0 0.5 1.0 2.0 ΔG 4.0 Breslow = 5.99σ P 8.27 ΔG r 2 = 0.95 Breslow 6.0 8.0 10.0 12.0 14.0 1.0 X = NMe 2 0.5 X = H X = OMe X = Br X = CF 3 X = CN 0.0 0.5 1.0 σ p Dipp N + N Dipp 6.0 H O X G Ketone Dipp N O N Dipp X 1.380 Dipp N r OH N Dipp X ΔG Ketone 6.5 7.0 X = NMe 2 ΔG Ketone = 0.90σ P 7.15 r 2 = 0.90 X = OMe r 1.375 1.370 r =0.0064σ P + 1.37 r 2 = 0.80 X = H X = CN X = CF 3 7.5 X = H X = Br X = CF 3 1.365 X = NMe 2 X = OMe X = Br 8.0 1.0 0.5 X = CN 0.0 0.5 1.0 σ p 1.360 1.0 0.5 0.0 0.5 1.0 σ p Figure S1: Correlation of the Hammett substituent constant σ p with the keto-enol energy difference (ΔΔG KE ), the reaction free energies ΔG Breslow and ΔG Ketone, (all in kcal mol 1 ) and the C-C double bond lengths r of the Breslow intermediate. (in Å). S3

3 Graphical Representations of the Lowest-Energy Structures of the Breslow Intermediates E-E-11 Z-E-11 E-21 E-31 E-41 E-51 E-61 E-E-71 Z-E-71 Figure S2: Lowest-energy structures for the Breslow intermediates E-11 E-71. S4

E-22 E-23 E-24 E-25 E-26 E-27 E-28 E-29 Figure S3: Lowest-energy structures for the Breslow intermediates E-22 E-29. S5

4 Graphical Representations of the Lowest-Energy Structures of the Ketone Tautomers K-11 K-21 K-31 K-41 K-51 K-61 K-71 Figure S2: Lowest-energy structures for the Breslow intermediates K-11 K-71. S6

K-22 K-23 K-24 K-25 K-26 K-27 K-28 K-29 Figure S3: Lowest-energy structures for the Breslow intermediates K-22 K-29. S7

5 Solvent-Dependence of the Keto-Enol-Energy Difference Table S1: Solvent-Dependence of the Keto-Enol-Energy Difference Dipp N OH ΔΔG KE Dipp N O Solvent N Ph Dipp Dielectric Constant G 298 (E-21) [hartree] N Ph Dipp E-21 K-21 G 298 (E-K1) [hartree] ΔΔG KE [kcal mol 1 ] Gas Phase 0.0 1506.114275 1506.110602 +2.3 Toluene 2.4 1506.118602 1506.114891 +2.3 THF 7.4 1506.122937 1506.119017 +2.5 Dichloroethane 10.1 1506.123738 1506.119753 +2.5 Benzaldehyde 18.2 1506.124858 1506.120765 +2.6 Acetonitrile 35.7 1506.125642 1506.121459 +2.6 Water 78.4 1506.126129 1506.121884 +2.7 S8

6 Coordinates and Calculated Energies for Free Carbenes 6.1 Carbene C-1 935.342141 hartree +0.301033 hartree +0.319371 hartree +0.253632 hartree +0.257707 hartree N 0.99525 1.03972-0.00894 N 1.70822-0.14494-0.00362 C -0.25075 0.64063-0.01882 N -0.29677-0.75257-0.01307 C 0.97201-1.28325-0.00926 C 3.12843-0.08491-0.00091 C -1.45750-1.57608 0.08529 C -2.45432-1.28023 1.01447 C -1.56242-2.69426-0.73961 C -3.57715-2.09855 1.09583 C -2.68427-3.51241-0.64260 C -3.69663-3.21376 0.26809 H -2.34861-0.41743 1.66563 H -4.35499-1.86790 1.81767 H -0.75749-2.91107-1.43461 H -2.76703-4.38509-1.28367 H -4.57242-3.85194 0.33815 C 3.77623 1.14958-0.04201 C 5.16809 1.18796-0.03902 C 5.91080 0.01047 0.00419 C 5.24898-1.21672 0.04496 C 3.86016-1.27343 0.04329 H 3.32766-2.21768 0.07640 H 5.81754-2.14167 0.07989 H 6.99613 0.04746 0.00619 H 5.67198 2.14977-0.07200 H 3.18814 2.05902-0.07787 C -1.37965 1.56701-0.09052 C -1.29514 2.79360 0.58277 C -2.33669 3.71122 0.50313 C -3.47219 3.41906-0.25132 C -3.55716 2.20620-0.93341 C -2.51955 1.28358-0.85625 H -2.58851 0.34546-1.39978 H -4.28652 4.13532-0.31112 H -4.43320 1.97781-1.53329 H -0.40479 3.01182 1.16500 H -2.26248 4.65639 1.03302 6.2 Carbene C-2 1161.166111 hartree +0.592869 hartree +0.624045 hartree S9

+0.533386 hartree +0.538309 hartree C 0.74051-0.16128 2.00785 N 1.07233 0.01033 0.57313 C -0.74041 0.16056 2.00793 H 1.34156 0.50250 2.63733 H 0.94998-1.19930 2.31091 N -1.07228-0.01033 0.57319 H -0.94974 1.19848 2.31148 H -1.34153-0.50339 2.63715 C 0.00001 0.00014-0.25024 C 2.41821-0.17401 0.13880 C -2.41815 0.17405 0.13888 C -2.84653 1.44362-0.28004 C -3.28486-0.93439 0.17733 C -4.18315 1.58470-0.66962 C -4.61236-0.74349-0.20902 C -5.05885 0.50735-0.62836 C -1.89484 2.61848-0.37742 H -4.53934 2.55439-1.01053 C -2.74494-2.30280 0.54333 H -5.30494-1.58053-0.19087 C 3.28491 0.93445 0.17723 C 4.61240 0.74354-0.20911 C 5.05891-0.50735-0.62832 C 4.18324-1.58472-0.66949 C 2.84659-1.44359-0.28000 C 1.89478-2.61834-0.37755 H 4.53945-2.55442-1.01035 H 5.30499 1.58058-0.19099 C 2.74495 2.30276 0.54343 H -0.98076 2.36532 0.17547 C -2.46672 3.89314 0.23712 C -1.49098 2.83982-1.83617 C -2.02061-2.91224-0.66083 C -3.80284-3.25953 1.07785 H -1.99195-2.16354 1.33219 H 0.98064-2.36508 0.17519 C 2.46643-3.89309 0.23698 C 1.49106-2.83952-1.83638 C 3.80294 3.25950 1.07779 H 1.99214 2.16327 1.33243 C 2.02036 2.91232-0.66049 H -6.09480 0.63892-0.92922 H 6.09487-0.63893-0.92915 H 4.36580 2.82712 1.91100 H 3.33517 4.18425 1.42858 H 4.52156 3.54217 0.30058 H 2.72840 3.10793-1.47393 H 1.54680 3.86387-0.39047 H 1.24684 2.23882-1.04467 H 1.00564-1.94639-2.24256 H 0.79569-3.68108-1.92675 H 2.37026-3.06240-2.45226 H 2.77449-3.74042 1.27651 H 3.33896-4.25688-0.31668 S10

H 1.71802-4.69224 0.21849 H -4.52169-3.54209 0.30082 H -4.36544-2.82719 1.91125 H -3.33503-4.18434 1.42842 H -2.72876-3.10738-1.47428 H -1.54730-3.86401-0.39116 H -1.24692-2.23884-1.04486 H -2.77488 3.74038 1.27660 H -3.33921 4.25687-0.31665 H -1.71838 4.69236 0.21875 H -1.00546 1.94677-2.24239 H -0.79570 3.68147-1.92643 H -2.37016 3.06267-2.45210 6.3 Carbene C-3 689.461269 hartree +0.255426 hartree +0.269745 hartree +0.214208 hartree +0.216131 hartree C 0.75949-1.90451 0.00004 N 1.07477-0.45947 0.00005 C -0.75950-1.90453-0.00006 H 1.18824-2.38639 0.88568 H 1.18842-2.38643-0.88549 N -1.07481-0.45947 0.00024 H -1.18830-2.38664 0.88544 H -1.18834-2.38621-0.88577 C 2.40905-0.01383 0.00003 C -2.40902-0.01392 0.00011 C -2.69779 1.35863 0.00016 C -3.46173-0.93719-0.00008 C -4.01744 1.78649 0.00005 C -4.78242-0.49097-0.00022 C -5.07093 0.86925-0.00012 H -1.87207 2.06124 0.00028 H -4.22642 2.85284 0.00002 H -3.26201-2.00404-0.00010 H -5.58715-1.22091-0.00039 H -6.10068 1.21330-0.00027 C 3.46168-0.93716 0.00004 C 4.78240-0.49103-0.00005 C 5.07093 0.86918-0.00014 C 4.01751 1.78648-0.00011 C 2.69782 1.35870-0.00002 H 1.87212 2.06132 0.00000 H 4.22659 2.85280-0.00016 H 6.10070 1.21319-0.00020 H 5.58709-1.22101-0.00005 H 3.26184-2.00400 0.00009 C -0.00002 0.35998 0.00018 S11

6.4 Carbene C-4 925.319383 hartree +0.419232 hartree +0.444420 hartree +0.363309 hartree +0.369829 hartree C 0.75521-0.07717 2.01690 N 1.07119 0.06629 0.57374 C -0.75517 0.07819 2.01688 H 1.27135 0.68161 2.61322 H 1.08387-1.06479 2.37065 N -1.07120-0.06599 0.57381 H -1.08382 1.06598 2.37016 H -1.27130-0.68030 2.61360 C -0.00002-0.00006-0.24721 C 2.42031 0.00114 0.12434 C -2.42033-0.00107 0.12440 C -3.26301-1.10234 0.32911 C -2.88965 1.16938-0.49741 C -4.59157-1.01263-0.09660 C -4.22096 1.21043-0.90992 C -5.08999 0.13187-0.71771 C -2.75109-2.35674 0.96929 H -5.24921-1.86860 0.05092 C -1.98046 2.33874-0.71801 H -4.59160 2.11444-1.39225 C -6.51357 0.20503-1.18241 C 2.88954-1.16949-0.49719 C 4.22084-1.21075-0.90968 C 5.08997-0.13222-0.71771 C 4.59165 1.01246-0.09687 C 3.26309 1.10238 0.32881 C 2.75131 2.35698 0.96871 H 5.24936 1.86840 0.05046 C 6.51357-0.20565-1.18233 H 4.59141-2.11490-1.39182 C 1.98029-2.33886-0.71750 H -2.75665-2.29226 2.06468 H -1.71953-2.56419 0.66676 H -3.36987-3.21606 0.69951 H -1.20430 2.10116-1.45280 H -1.45105 2.61841 0.20008 H -2.53982 3.20973-1.06825 H -7.01971 1.09411-0.79225 H -7.08553-0.67083-0.86564 H -6.57593 0.26208-2.27472 H 2.75733 2.29292 2.06413 H 1.71962 2.56425 0.66650 H 3.36993 3.21625 0.69836 H 1.45069-2.61811 0.20061 H 2.53963-3.21004-1.06730 H 1.20426-2.10151-1.45252 S12

H 7.01984-1.09425-0.79123 H 7.08540 0.67062-0.86645 H 6.57596-0.26384-2.27458 6.5 Carbene C-5 1159.968415 hartree +0.570004 hartree +0.600624 hartree +0.511018 hartree +0.515972 hartree C 0.67674-0.03552 1.93555 N 1.05874-0.05267 0.59855 C -0.67678 0.03810 1.93552 N -1.05879 0.05337 0.59850 C -0.00005-0.00028-0.27257 C 2.42451-0.15316 0.17599 C -2.42464 0.15329 0.17599 C -2.90248 1.39469-0.26830 C -3.23086-0.99764 0.23186 C -4.24251 1.46551-0.66378 C -4.56418-0.87171-0.16349 C -5.06635 0.34870-0.60674 C -2.00103 2.60670-0.38351 H -4.64273 2.41154-1.02029 C -2.63881-2.33712 0.62544 H -5.21693-1.73945-0.13137 C 3.23132 0.99738 0.23195 C 4.56458 0.87086-0.16340 C 5.06615-0.34971-0.60690 C 4.24175-1.46608-0.66412 C 2.90177-1.39469-0.26857 C 2.00007-2.60654-0.38357 H 4.64145-2.41227-1.02081 H 5.21776 1.73826-0.13116 C 2.63990 2.33721 0.62536 H -1.10621 2.42296 0.22539 C -2.65552 3.88510 0.13236 C -1.54264 2.77228-1.83415 C -1.90173-2.94854-0.57043 C -3.66099-3.31768 1.18635 H -1.89007-2.15603 1.40833 H 1.10486-2.42221 0.22456 C 2.65404-3.88466 0.13374 C 1.54266-2.77315-1.83438 C 3.66268 3.31780 1.18512 H 1.89166 2.15674 1.40886 C 1.90216 2.94825-0.57030 H -6.10611 0.42609-0.91297 H 6.10586-0.42753-0.91319 H 4.23968 2.88595 2.00882 H 3.15959 4.21463 1.55841 H 4.37109 3.64769 0.41719 S13

H 2.60783 3.18543-1.37489 H 1.39589 3.87700-0.28162 H 1.15294 2.25917-0.97452 H 1.00090-1.88508-2.17515 H 0.88299-3.64157-1.93771 H 2.40423-2.92527-2.49525 H 3.01985-3.77076 1.15884 H 3.50079-4.19161-0.49002 H 1.93281-4.70827 0.12068 H -4.36992-3.64796 0.41906 H -4.23747-2.88563 2.01031 H -3.15751-4.21431 1.55959 H -2.60784-3.18599-1.37454 H -1.39531-3.87720-0.28170 H -1.15272-2.25957-0.97523 H -3.02218 3.77189 1.15723 H -3.50175 4.19158-0.49234 H -1.93433 4.70874 0.11933 H -1.00062 1.88400-2.17398 H -0.88295 3.64067-1.93768 H -2.40380 2.92388-2.49567 H 1.39124-0.07848 2.74410 H -1.39130 0.08185 2.74401 6.6 Carbene C-6 688.255936 hartree +0.231683 hartree +0.245421 hartree +0.190929 hartree +0.193086 hartree C -0.67603-1.79031 0.42364 N -1.06367-0.48401 0.13490 C 0.67603-1.79031 0.42364 N 1.06367-0.48401 0.13490 C -2.41473-0.06066 0.01926 C 2.41473-0.06066 0.01926 C 2.72895 1.28958 0.18725 C 3.42176-0.98452-0.26440 C 4.05051 1.70505 0.07412 C 4.74346-0.55756-0.36587 C 5.06480 0.78662-0.19716 H 1.92548 1.98751 0.39620 H 4.28991 2.75633 0.20649 H 3.17642-2.02919-0.43022 H 5.52116-1.28203-0.58970 H 6.09588 1.11694-0.27937 C -3.42176-0.98451-0.26443 C -4.74346-0.55756-0.36590 C -5.06480 0.78662-0.19715 C -4.05051 1.70505 0.07415 C -2.72896 1.28957 0.18728 H -1.92549 1.98750 0.39625 S14

H -4.28992 2.75632 0.20654 H -6.09588 1.11694-0.27937 H -5.52116-1.28202-0.58975 H -3.17640-2.02918-0.43027 C 0.00000 0.36409-0.05126 H 1.37291-2.58299 0.64497 H -1.37291-2.58298 0.64497 6.7 Carbene C-7 800.040009 hartree +0.135403 hartree +0.144770 hartree +0.101161 hartree +0.101542 hartree C -1.36881 1.19257 0.39822 N -0.67766 0.03687 0.01599 C -2.70670 1.02665 0.33398 S -3.03616-0.59217-0.20651 C 0.75687 0.00707 0.00472 C 1.48352 1.16381-0.27651 C 2.87580 1.11739-0.28075 C 3.54049-0.07686-0.01506 C 2.80389-1.23058 0.25245 C 1.41410-1.19479 0.26527 H 0.82007-2.08049 0.46387 H 3.31415-2.16685 0.45870 H 4.62577-0.11007-0.02072 H 3.43841 2.01861-0.50586 H 0.96991 2.08913-0.51978 C -1.39171-1.06390-0.34927 H -3.46675 1.75256 0.58556 H -0.82406 2.06545 0.73208 S15

7 Coordinates and Calculated Energies for Free Aldehydes 7.1 Aldehyde A-1 345.561934 hartree +0.109692 hartree +0.116968 hartree +0.079125 hartree +0.079125 hartree C 1.72781 1.06350-0.00002 C 0.35466 1.28670 0.00001 C 2.21288-0.24381-0.00002 C 1.32919-1.32698 0.00001 C -0.04089-1.10505 0.00003 C -0.53467 0.20671 0.00003 H 2.41888 1.90116-0.00006 H -0.04217 2.30067 0.00003 H 1.71669-2.34164 0.00002 H 3.28472-0.42176-0.00005 H -0.75252-1.92616 0.00004 C -1.98317 0.46512 0.00004 O -2.84564-0.39229-0.00006 H -2.25538 1.54887 0.00006 7.2 Aldehyde A-2 437.811171 hartree +0.108151 hartree +0.117235 hartree +0.074794 hartree +0.075029 hartree C 0.00952-1.52146 0.00000 C -1.19327-0.82973 0.00000 C 1.21561-0.80371 0.00000 C 1.20670 0.60327 0.00000 C 0.00000 1.28150 0.00000 C -1.20656 0.56889 0.00000 H 0.03136-2.60618 0.00000 H -2.13615-1.37276 0.00000 H 2.14872 1.14192 0.00000 C 2.45849-1.50551 0.00000 H -0.03755 2.36696 0.00000 C -2.49707 1.28407 0.00000 O -2.61288 2.49310 0.00000 H -3.39384 0.62010 0.00000 N 3.47570-2.07984 0.00000 S16

7.3 Aldehyde A-3 682.652946 hartree +0.114111 hartree +0.125005 hartree +0.077053 hartree +0.078739 hartree C 0.09484 1.30876-0.00002 C -1.29476 1.37993-0.00015 C 0.71109 0.05970-0.00007 C -0.04997-1.11623-0.00025 C -1.43226-1.03983-0.00038 C -2.06187 0.21274-0.00034 H 0.69818 2.21010 0.00012 H -1.79405 2.34678-0.00012 H 0.45164-2.07967-0.00029 C 2.20677-0.06108 0.00009 H -2.05055-1.93282-0.00054 C -3.53376 0.31194-0.00056 O -4.28947-0.63926 0.00078 H -3.92562 1.35704 0.00100 F 2.82518 1.13578 0.00025 F 2.64839-0.74130-1.08369 F 2.64816-0.74147 1.08385 7.4 Aldehyde A-4 2919.158342 hartree +0.100423 hartree +0.108855 hartree +0.066897 hartree +0.066974 hartree C 0.05544 1.29373 0.00000 C -1.33166 1.36916 0.00000 C 0.65864 0.03688 0.00001 C -0.09943-1.13745 0.00000 C -1.48208-1.04751 0.00000 C -2.10793 0.20605-0.00000 H 0.66558 2.19050 0.00000 H -1.82381 2.34005-0.00000 H 0.39772-2.10161 0.00000 Br 2.53751-0.08426-0.00000 H -2.10292-1.93908 0.00000 C -3.57416 0.31076-0.00000 O -4.33762-0.63606-0.00000 H -3.96136 1.35812-0.00000 S17

7.5 Aldehyde A-5 460.093076 hartree +0.142319 hartree +0.152069 hartree +0.108442 hartree +0.108721 hartree C -0.83760 1.03603-0.00000 C 0.53174 1.27678-0.00000 C -1.29332-0.28815-0.00000 C -0.37716-1.35510-0.00000 C 0.97772-1.09787-0.00000 C 1.45243 0.22595-0.00000 H -1.53483 1.86620-0.00000 H 0.89835 2.30215-0.00000 H -0.76634-2.36815-0.00000 O -2.59983-0.64319-0.00000 H 1.70231-1.90745-0.00000 C 2.88662 0.51566-0.00000 O 3.77346-0.32016 0.00001 H 3.13253 1.60611 0.00000 C -3.56388 0.39618 0.00001 H -4.53484-0.09687 0.00001 H -3.47277 1.02396-0.89427 H -3.47276 1.02396 0.89428 7.6 Aldehyde A-6 479.528030 hartree +0.182473 hartree +0.194219 hartree +0.145290 hartree +0.146651 hartree C 0.34817 1.27856 0.00005 C -1.03245 1.36110 0.00001 C 0.98739 0.01594 0.00011 C 0.17301-1.14561 0.00007 C -1.20261-1.04114 0.00003 C -1.83520 0.21268 0.00001 H 0.93712 2.18878 0.00003 H -1.51090 2.33963-0.00004 H 0.63095-2.12858 0.00007 N 2.35488-0.08362 0.00021 H -1.82494-1.93218 0.00001 C -3.28772 0.33087-0.00005 O -4.07615-0.60187-0.00006 H -3.65885 1.38597-0.00008 C 3.16827 1.11122-0.00010 H 4.22062 0.82878-0.00000 H 2.98277 1.73072 0.88719 S18

H 2.98279 1.73031-0.88769 C 2.99026-1.38251-0.00012 H 2.71948-1.96891-0.88774 H 2.71929-1.96938 0.88712 H 4.07193-1.25147 0.00006 7.7 Aldehyde A-7 1019.737345 hartree +0.118999 hartree +0.133432 hartree +0.077196 hartree +0.079273 hartree C -1.14370 1.68126-0.00772 C 0.19292 2.05714-0.00367 C -1.47151 0.32795-0.00896 C -0.47097-0.64468-0.00566 C 0.86491-0.26451-0.00181 C 1.21162 1.10110-0.00062 H -1.92888 2.42932-0.01154 H 0.48383 3.10323-0.00334 H -0.73610-1.69638-0.00788 C -2.90302-0.12617-0.00029 C 1.92686-1.33102-0.00039 C 2.61820 1.58974 0.00307 O 2.89436 2.77297 0.00407 H 3.41630 0.82376 0.00510 F -3.76736 0.90017-0.10178 F -3.19895-0.79262 1.13883 F -3.15742-0.97412-1.02156 F 1.40565-2.57040-0.00250 F 2.73121-1.23555-1.08521 F 2.72665-1.23731 1.08791 7.8 Aldehyde A-8 343.354081 hartree +0.079428 hartree +0.085919 hartree +0.049956 hartree +0.049956 hartree C 1.58749-0.89558 0.00000 O 0.24441-1.00524-0.00001 C 1.97881 0.41548 0.00001 C 0.78262 1.17125 0.00001 C -0.25476 0.26793-0.00002 C -1.68659 0.46882-0.00005 H 2.12937-1.82900 0.00000 S19

H 2.99475 0.78145 0.00002 O -2.53012-0.40928 0.00003 H 0.68010 2.24769 0.00002 H -1.96401 1.54869 0.00005 7.9 Aldehyde A-9 422.959016 hartree +0.143047 hartree +0.152588 hartree +0.108781 hartree +0.109261 hartree C -2.79678-0.99370-0.00000 C -1.43555-1.27587-0.00000 C -3.23156 0.33009-0.00000 C -2.29716 1.36858-0.00000 C -0.93868 1.08739 0.00000 C -0.48208-0.24341 0.00000 H -1.09277-2.30832 0.00000 C 0.92758-0.58681 0.00001 H -3.51847-1.80516-0.00001 H -4.29411 0.55486-0.00001 H -0.22065 1.90282 0.00000 H -2.63381 2.40114-0.00001 C 1.98887 0.24957 0.00002 H 1.14753-1.65813-0.00000 H 1.88580 1.33249 0.00003 C 3.34119-0.28496 0.00003 O 4.36007 0.38467-0.00003 H 3.39094-1.40241-0.00006 S20

8 Coordinates and Calculated Energies for Breslow Intermediates 8.1 Breslow Intermediate E-E-11 1280.921954 hartree +0.413517 hartree +0.439417 hartree +0.356680 hartree +0.363462 hartree C -1.48950-0.98393 0.05791 N 0.64750-1.03198 0.06736 N -0.48972-1.79871-0.11802 N -1.07576 0.31084 0.37600 C -2.87699-1.43150-0.01717 C -3.90843-0.81157 0.70323 C -3.17616-2.55009-0.81024 C -5.20824-1.30093 0.62546 H -3.69379 0.04433 1.33524 C -4.47625-3.03318-0.88270 H -2.37285-3.02806-1.36271 C -5.49901-2.40833-0.16854 H -5.99659-0.81376 1.19188 H -4.69400-3.89813-1.50259 H -6.51659-2.78304-0.23073 C 1.85699-1.70717 0.33055 C 2.12657-2.89074-0.36393 C 2.77733-1.21530 1.26128 C 3.32124-3.56480-0.13745 H 1.39238-3.26733-1.06837 C 3.97052-1.89647 1.47185 H 2.56273-0.30132 1.80464 C 4.25438-3.06837 0.77238 H 3.52653-4.48086-0.68429 H 4.68363-1.50222 2.19035 H 5.19250-3.59012 0.93551 C -1.89703 1.46040 0.14228 C -2.42224 1.67554-1.13042 C -2.21699 2.31778 1.19408 C -3.28097 2.75144-1.35012 H -2.16553 0.99291-1.93658 C -3.06860 3.39250 0.96765 H -1.78490 2.13653 2.17291 C -3.60535 3.60993-0.30317 H -3.69632 2.91403-2.34030 H -3.31899 4.06074 1.78644 H -4.27690 4.44626-0.47368 C 0.33226 0.31433 0.25315 C 1.16660 1.40124 0.25584 O 0.66851 2.54019 0.88824 H 0.83478 3.29816 0.31423 C 2.53540 1.44682-0.22141 C 2.99320 0.63924-1.28321 C 3.45022 2.35169 0.35307 C 4.30837 0.70677-1.71838 H 2.30268-0.04546-1.76883 S21

C 4.76607 2.42102-0.09344 H 3.12119 2.97940 1.17722 C 5.20870 1.59481-1.12515 H 4.63341 0.06493-2.53316 H 5.45387 3.11915 0.37699 H 6.23808 1.64463-1.46767 8.2 Breslow Intermediate Z-E-11 1280.921987 hartree +0.413577 hartree +0.439375 hartree +0.357848 hartree +0.363391 hartree C -0.53402 1.66933-0.09610 N 1.51834 1.10189-0.28429 N 0.65305 2.18170-0.24366 N -0.49893 0.27897-0.03063 C -1.73123 2.51073-0.01913 C -2.94006 2.17627-0.64687 C -1.63183 3.73329 0.66149 C -4.02674 3.04234-0.57726 H -3.03020 1.24990-1.20537 C -2.72140 4.59365 0.72716 H -0.68903 3.99269 1.13362 C -3.92466 4.24844 0.11303 H -4.95566 2.77362-1.07171 H -2.63199 5.53432 1.26271 H -4.77772 4.91860 0.16831 C 2.88699 1.34857-0.06767 C 3.44325 2.53565-0.55492 C 3.67436 0.45775 0.67047 C 4.78439 2.81370-0.32069 H 2.81257 3.22517-1.10536 C 5.01517 0.75061 0.89717 H 3.22184-0.43384 1.09465 C 5.58112 1.92260 0.39868 H 5.21118 3.73428-0.70880 H 5.61793 0.05921 1.47979 H 6.62982 2.14236 0.57410 C -1.62992-0.58332-0.08898 C -1.81886-1.42045-1.18891 C -2.54861-0.56909 0.95944 C -2.93529-2.24903-1.23130 H -1.08216-1.43044-1.98700 C -3.67265-1.38776 0.90004 H -2.37879 0.08907 1.80739 C -3.86496-2.23266-0.19135 H -3.07833-2.91027-2.08082 H -4.39218-1.37215 1.71334 H -4.73437-2.88215-0.23010 C 0.84083-0.11105-0.21430 C 1.36219-1.36411-0.45436 S22

O 2.52000-1.37107-1.22531 H 3.21856-1.84778-0.75602 C 0.81673-2.63733-0.03732 C 1.06836-3.79951-0.79554 C 0.06507-2.77961 1.14823 C 0.55229-5.03087-0.40795 H 1.65311-3.71174-1.70746 C -0.46109-4.00819 1.52102 H -0.09417-1.90955 1.78140 C -0.22628-5.14493 0.74435 H 0.75079-5.90900-1.01741 H -1.04544-4.08415 2.43481 H -0.63200-6.10741 1.04181 8.3 Breslow Intermediate E-21 1506.767980 hartree +0.706176 hartree +0.744959 hartree +0.637156 hartree +0.645042 hartree O -1.23581 0.47000 1.90514 N -1.46408 0.09917-0.82389 N 0.76687-0.06595-1.09373 C -0.14147-0.06212 1.21374 C -0.26129-0.04893-0.15112 C -1.24236 0.34285-2.24385 C 0.19280-0.13500-2.44250 C 2.01194 0.60132-0.88380 C 2.04972 1.92943-0.41173 C 3.30064 2.49700-0.15493 C 4.47772 1.80099-0.40401 C 4.42083 0.51890-0.93772 C 3.19563-0.10586-1.17870 C 3.15071-1.49210-1.79020 C 3.33591-1.41667-3.30859 C 4.17700-2.44798-1.18916 C 0.81140 2.79119-0.24982 C 0.83950 3.96371-1.23202 C 0.62730 3.28100 1.18437 C -2.70528-0.40326-0.34207 C -2.88686-1.78875-0.17575 C -4.12624-2.23440 0.29580 C -5.15583-1.34169 0.57043 C -4.95576 0.02400 0.39359 C -3.72707 0.51770-0.04798 C -3.50244 2.00845-0.18928 C -4.26448 2.56678-1.39174 C -3.86471 2.76357 1.08686 C -1.80159-2.80174-0.48578 C -1.33722-3.51691 0.78256 C -2.25732-3.80305-1.54665 C 1.01262-0.44008 2.00671 S23

C 1.16619 0.08728 3.30600 C 2.23873-0.27962 4.11091 C 3.18748-1.19226 3.65373 C 3.03728-1.74123 2.37908 C 1.96907-1.37959 1.56911 H -1.55455-0.19053 2.53405 H -1.35832 1.41221-2.49026 H -1.96652-0.21979-2.84213 H 0.22679-1.16405-2.83471 H 0.76528 0.50450-3.12022 H 3.34824 3.51641 0.22346 H 5.43885 2.26410-0.19873 H 5.34350-0.01436-1.15413 H 2.15136-1.90388-1.59043 H 2.59993-0.75993-3.78236 H 3.24885-2.40841-3.76554 H 4.32890-1.02210-3.55318 H 5.20139-2.15464-1.44322 H 4.02852-3.46150-1.57491 H 4.10441-2.48302-0.09870 H -0.06946 2.19545-0.50095 H 1.67267 4.64423-1.02356 H -0.08795 4.54367-1.16160 H 0.94673 3.61952-2.26667 H 0.61597 2.44706 1.89118 H -0.32067 3.82096 1.28737 H 1.43408 3.96295 1.47740 H -4.28693-3.30158 0.43815 H -6.11440-1.71018 0.92570 H -5.76027 0.72065 0.62079 H -2.42888 2.15919-0.36142 H -3.99568 2.05025-2.31936 H -4.05760 3.63395-1.52604 H -5.34660 2.45293-1.25653 H -4.93277 2.67976 1.31790 H -3.63866 3.82959 0.97756 H -3.29900 2.38216 1.94127 H -0.93427-2.26837-0.89117 H -0.96572-2.80436 1.52650 H -0.52540-4.21793 0.56110 H -2.15573-4.08728 1.23671 H -3.10595-4.40124-1.19673 H -1.44806-4.49714-1.79613 H -2.56888-3.29946-2.46790 H 0.43642 0.80709 3.66697 H 2.33552 0.15537 5.10252 H 4.02435-1.48213 4.28219 H 3.75519-2.47636 2.02251 H 1.84712-1.84394 0.59247 8.4 Breslow Intermediate E-31 1035.055534 hartree +0.368841 hartree +0.390393 hartree +0.318298 hartree S24

+0.322855 hartree C -0.51706-0.38387-0.12485 C -1.64110-2.42750-0.13394 C -0.42696-2.52918 0.77746 N 0.35639-1.35943 0.37380 H -1.46608-2.93068-1.09454 H 0.15715-3.43899 0.62524 H -2.55148-2.83219 0.31290 H -0.71662-2.46971 1.83592 C -3.00632-0.35131-0.08588 C -3.12258 0.85322 0.62346 C -4.17167-0.96933-0.56313 C -4.37463 1.41614 0.84303 C -5.41881-0.39825-0.33427 C -5.53169 0.80088 0.36651 H -4.44488 2.34382 1.40501 H -6.30716-0.89240-0.71811 H -6.50523 1.24908 0.53920 C 1.71349-1.50892 0.02574 C 2.26913-0.94018-1.12846 C 2.53935-2.25002 0.88282 C 3.62214-1.10296-1.40122 C 3.88961-2.41742 0.59252 C 4.44355-1.83802-0.54680 H 4.03610-0.65092-2.29843 H 4.51299-2.99101 1.27300 H 5.50052-1.95476-0.76542 N -1.76981-0.97879-0.31003 C -0.20368 0.90740-0.44750 O -1.07162 1.52650-1.33538 H -1.27059 2.41397-1.01038 C 0.98271 1.64221-0.04059 C 1.46818 2.68897-0.84740 C 1.67106 1.36219 1.15692 C 2.60665 3.40304-0.48595 H 0.95889 2.91363-1.78103 C 2.80968 2.07225 1.50833 H 1.30263 0.57726 1.81173 C 3.29016 3.09604 0.68873 H 2.96751 4.19771-1.13383 H 3.32497 1.83004 2.43411 H 4.18274 3.64890 0.96645 H 2.11871-2.67730 1.78995 H 1.64234-0.36501-1.80158 H -4.09227-1.89189-1.13199 H -2.23051 1.32377 1.02525 8.5 Breslow Intermediate E-41 1270.924567 hartree +0.533643 hartree +0.565475 hartree +0.470676 hartree S25

+0.478696 hartree C -0.37943-0.38196-0.03081 C -1.29783-2.52189 0.17044 C -0.01820-2.44747 0.99603 N 0.60000-1.20932 0.51563 H -2.14242-2.94499 0.72142 H 0.65823-3.28955 0.82778 H -1.15272-3.11486-0.74683 H -0.23880-2.39426 2.07413 C -2.84792-0.54872 0.01086 C -3.17573 0.22417 1.13698 C -3.79663-0.79837-0.99600 C -4.46929 0.75111 1.22087 C -5.07685-0.26647-0.86020 C -5.43360 0.51905 0.24059 H -4.73268 1.34798 2.09371 H -5.81002-0.45403-1.64413 C 1.97793-1.15823 0.17586 C 2.40756-1.02543-1.15927 C 2.91165-1.23815 1.22536 C 3.77829-0.91180-1.39891 C 4.27123-1.14455 0.92891 C 4.72715-0.95563-0.37579 H 4.11460-0.80466-2.42984 H 4.99073-1.19467 1.74553 N -1.55371-1.11622-0.14145 C -0.22910 0.90401-0.47397 O -1.17716 1.32304-1.41165 H -1.55548 2.15962-1.11439 C 0.88575 1.79327-0.20814 C 1.25318 2.77267-1.15296 C 1.61306 1.74653 0.99847 C 2.32342 3.62930-0.91705 H 0.70109 2.83111-2.08758 C 2.68621 2.59604 1.22458 H 1.31838 1.03192 1.76277 C 3.05556 3.54277 0.26671 H 2.59436 4.36518-1.67017 H 3.23474 2.52466 2.16120 H 3.89466 4.20874 0.44593 C -2.19312 0.48476 2.23894 H -1.56899-0.39195 2.44663 C -3.40529-1.59040-2.20395 H -3.22542-2.64598-1.96568 C 1.46044-1.02868-2.32103 H 1.96766-1.38892-3.22031 C 2.45369-1.39893 2.64275 H 3.24617-1.12970 3.34558 H 1.57656-0.77537 2.85267 H 2.15728-2.43119 2.86880 H 1.06961-0.02800-2.53785 H 0.58917-1.66783-2.14337 H -1.50015 1.29660 1.98708 H -2.71033 0.76010 3.16174 H -2.47291-1.20184-2.62886 H -4.18282-1.55590-2.97071 S26

C 6.18638-0.78595-0.67159 H 6.45349 0.27459-0.74742 H 6.81150-1.22089 0.11299 H 6.46355-1.25119-1.62222 C -6.81656 1.08509 0.36259 H -7.57120 0.29382 0.42990 H -6.91653 1.71320 1.25145 H -7.07982 1.69583-0.50755 8.6 Breslow Intermediate E-51 1505.554591 hartree +0.682792 hartree +0.720845 hartree +0.615953 hartree +0.622480 hartree C 0.01647 0.63327-2.28877 C -1.31669 0.54973-2.13281 N -1.57959 0.00927-0.86979 N 0.62703 0.15252-1.12511 C -0.36463-0.18881-0.19982 H 0.61416 0.91995-3.13910 H -2.12340 0.81432-2.79827 C -0.24219-0.69673 1.07408 O -1.33383-1.46213 1.51013 C 0.94342-0.69258 1.90213 C 1.24458-1.79055 2.73482 C 1.81075 0.41819 1.94954 C 2.95885 0.40425 2.72807 C 3.26120-0.70530 3.52093 C 2.38685-1.79328 3.52730 H 0.57957-2.65087 2.72369 H 1.55418 1.30018 1.36623 H 3.61723 1.27059 2.72982 H 4.15679-0.71431 4.13517 H 2.60492-2.65933 4.14770 C -2.77986 0.35325-0.16065 C -3.81678-0.59165-0.10062 C -4.98932-0.22479 0.56188 C -5.11227 1.02763 1.15954 C -4.06002 1.93331 1.10847 C -2.86851 1.61578 0.44646 C -1.72737 2.61406 0.42270 C -3.64295-1.95513-0.73490 H -5.81197-0.93200 0.62642 H -4.15888 2.90534 1.58795 H -6.03157 1.29326 1.67464 C 2.03586-0.05925-1.03111 C 2.54212-1.37426-0.94810 C 3.92722-1.52155-0.84930 C 4.77904-0.42091-0.86855 C 4.25665 0.86025-0.97095 C 2.87626 1.07001-1.03364 S27

C 1.62556-2.58322-1.00713 H 5.85342-0.56713-0.79898 H 4.35181-2.51688-0.76555 C 2.33632 2.48802-1.08388 H 4.92590 1.71779-0.97526 C -4.39049-3.05611 0.00669 H -4.13483-3.06625 1.07052 H -4.13343-4.03425-0.41072 H -5.47767-2.94734-0.08038 C -2.14187 3.93912-0.21371 H -0.92097 2.20280-0.19369 C -1.15922 2.82884 1.82523 H -2.52985 3.79409-1.22696 H -1.28409 4.61831-0.27399 H -2.91911 4.44296 0.37185 H -1.90710 3.27082 2.49371 H -0.29824 3.50667 1.79469 H -0.82577 1.88313 2.26605 C -4.04406-1.92532-2.21065 H -3.45815-1.19196-2.77375 H -5.10313-1.66537-2.32401 H -3.88697-2.90364-2.67699 H -2.57230-2.18851-0.68195 H 0.78900-2.39783-0.32207 C 2.29088-3.87536-0.55012 C 1.03585-2.76297-2.40992 H 0.46419-1.88965-2.73811 H 0.36053-3.62507-2.42972 H 1.82845-2.94324-3.14553 H 2.74332-3.77292 0.44108 H 3.06904-4.20633-1.24792 H 1.54655-4.67521-0.49708 C 2.95395 3.38854-0.01356 H 1.25540 2.44652-0.89388 C 2.54998 3.11213-2.46456 H 3.62019 3.20144-2.68421 H 2.11418 4.11561-2.51178 H 2.10387 2.51418-3.26464 H 2.84987 2.96821 0.99095 H 2.46862 4.37020-0.01939 H 4.02166 3.55462-0.19287 H -1.63033-1.11005 2.35901 8.7 Breslow Intermediate E-61 1033.837587 hartree +0.344489 hartree +0.365623 hartree +0.295144 hartree +0.298800 hartree C 1.68105-2.43972 0.13191 C 0.38522-2.70437 0.36373 N -0.34574-1.52105 0.20367 S28

N 1.80910-1.07344-0.15440 C 0.54052-0.48124-0.11318 H 2.54821-3.07637 0.19099 H -0.11568-3.63343 0.58201 C 0.24555 0.83127-0.41886 O 1.16776 1.45940-1.25305 C -0.94244 1.56352-0.04522 C -1.38917 2.64521-0.83304 C -1.67903 1.25852 1.12071 C -2.82688 1.96300 1.44959 C -3.27015 3.01612 0.64507 C -2.53466 3.35572-0.49016 H -0.83746 2.89861-1.73445 H -1.33567 0.45791 1.77195 H -3.37683 1.69675 2.34895 H -4.16836 3.56801 0.90583 H -2.86246 4.17638-1.12363 C -1.74412-1.54407-0.03734 C -2.30163-0.94278-1.16860 C -3.67778-0.98329-1.35856 C -4.50417-1.63061-0.43993 C -3.94176-2.24494 0.67660 C -2.56605-2.19646 0.88430 H -2.12339-2.64243 1.77159 H -1.65905-0.43127-1.87786 H -4.10654-0.50347-2.23368 H -4.57503-2.74831 1.40154 H -5.57902-1.65134-0.59206 C 3.04641-0.40374-0.01188 C 3.15660 0.77943 0.72654 C 4.40113 1.37695 0.89131 C 5.54421 0.80756 0.33053 C 5.43121-0.37505-0.39798 C 4.18998-0.97848-0.57349 H 2.26875 1.20383 1.18731 H 6.51234 1.28154 0.45976 H 4.47855 2.29113 1.47352 H 4.09781-1.88588-1.16420 H 6.31161-0.82681-0.84599 H 1.47235 2.27599-0.83442 8.8 Breslow Intermediate E-E-71 1145.637022 hartree +0.248608 hartree +0.265502 hartree +0.204453 hartree +0.206727 hartree C 1.75345 2.30023-0.35931 C 0.77757 3.19213-0.13571 S -0.75240 2.41640 0.21719 N 1.35752 0.96571-0.27537 C -0.03068 0.82113-0.09663 S29

H 2.79954 2.51516-0.52703 H 0.86875 4.26682-0.10806 C -0.73301-0.32413-0.36560 O -0.02690-1.33227-0.99334 C -2.15176-0.53248-0.14992 C -2.83668-1.50320-0.91134 C -2.88910 0.18048 0.81672 C -4.25023-0.04191 0.98529 C -4.91594-0.99311 0.21262 C -4.19612-1.72531-0.73169 H -2.29604-2.05558-1.67484 H -2.38399 0.88185 1.47472 H -4.79160 0.52001 1.74162 H -5.97900-1.16691 0.34997 H -4.70046-2.46999-1.34179 C 2.31227-0.04933-0.01125 C 2.07558-1.02075 0.96622 C 3.04457-1.97844 1.23953 C 4.25778-1.97960 0.55083 C 4.49003-1.00993-0.42219 C 3.52311-0.05112-0.70963 H 1.13549-1.00731 1.51064 H 5.01136-2.73019 0.76823 H 2.85297-2.72462 2.00579 H 3.69568 0.68210-1.49238 H 5.42501-1.00414-0.97518 H -0.27184-2.17941-0.60000 8.9 Breslow Intermediate Z-E-71 1145.639749 hartree +0.248718 hartree +0.265500 hartree +0.205065 hartree +0.207042 hartree C -2.59181 1.42538 0.53144 C -3.68746 0.66411 0.38722 S -3.30177-0.96925-0.11488 N -1.38761 0.77407 0.25117 C -1.57153-0.59586 0.00202 H -2.55683 2.47970 0.77001 H -4.71253 0.97822 0.51060 C -0.63562-1.58063-0.11624 O -1.13985-2.76310-0.64728 C 0.78533-1.52234 0.17412 C 1.68939-2.30558-0.56937 C 1.30290-0.72309 1.21275 C 2.66614-0.67905 1.46611 C 3.55362-1.44383 0.70583 C 3.05473-2.26277-0.30599 H 1.31048-2.92163-1.38122 H 0.62085-0.14026 1.82571 H 3.04011-0.04873 2.26872 S30

H 4.62042-1.40576 0.90557 H 3.73456-2.86457-0.90343 C -0.23728 1.51859-0.12326 C 0.48794 1.19847-1.27457 C 1.62229 1.93103-1.60110 C 2.04062 2.99167-0.79702 C 1.30779 3.31672 0.34209 C 0.17722 2.58055 0.68604 H 0.16812 0.36717-1.89528 H 2.93187 3.55570-1.05415 H 2.18310 1.67013-2.49411 H -0.37334 2.80897 1.59518 H 1.62477 4.13600 0.98117 H -0.71666-3.50090-0.19121 8.10 Breslow Intermediate E-22 1599.023880 hartree +0.705745 hartree +0.745952 hartree +0.635412 hartree +0.643090 hartree C -0.58252-0.21691 0.19526 C -1.99562-0.52958 2.03226 C -0.64246-0.03252 2.52873 N 0.20548-0.14749 1.33976 H -2.14181-1.59651 2.26020 H -0.23067-0.64772 3.33447 H -2.83876 0.02694 2.45025 H -0.69246 1.00784 2.88965 C -2.94017 0.46402-0.06561 C -4.06513-0.21649-0.57038 C -2.82123 1.86471-0.17080 C -5.07841 0.52944-1.17672 C -3.85167 2.56335-0.80631 C -4.97304 1.90928-1.30153 H -5.95575 0.01888-1.56719 H -3.77382 3.64451-0.90293 H -5.76439 2.47504-1.78512 C 1.53608-0.64666 1.44205 C 1.83247-1.97431 1.07878 C 2.53407 0.23057 1.91511 C 3.16966-2.37881 1.12502 C 3.84826-0.23473 1.98094 C 4.17152-1.52110 1.56392 H 3.42377-3.39647 0.83519 H 4.63297 0.42735 2.33930 H 5.20323-1.85960 1.59272 N -1.92336-0.31786 0.58153 C -0.19838-0.32390-1.11916 O -1.12548-0.80958-2.03687 H -1.76347-1.35364-1.55656 C 1.08045-0.00172-1.69870 S31

C 1.48071-0.61086-2.90865 C 1.94955 0.95204-1.12777 C 2.71461-0.34197-3.47225 H 0.80386-1.30897-3.38970 C 3.18535 1.22101-1.68340 H 1.62573 1.49975-0.24728 C 3.59546 0.56626-2.85905 H 3.01422-0.83575-4.39168 H 3.84648 1.95138-1.22511 C -4.20167-1.72171-0.45334 H -3.21701-2.12193-0.16971 C -1.64735 2.64739 0.38511 H -0.96767 1.95379 0.88511 C 0.76677-2.99597 0.72855 H -0.20886-2.49796 0.72426 C 2.18957 1.63691 2.36776 H 1.20647 1.88559 1.94116 C -4.61498-2.37465-1.77113 H -4.60232-3.46514-1.68031 H -5.63107-2.08737-2.06125 H -3.94986-2.09325-2.59384 C -5.17865-2.09277 0.66388 H -5.24892-3.17903 0.78170 H -4.87652-1.66542 1.62534 H -6.18255-1.71518 0.43866 C -2.09353 3.66283 1.43706 H -2.72983 4.44215 1.00391 H -2.66025 3.18666 2.24456 H -1.22313 4.15936 1.88104 C -0.85003 3.32185-0.73054 H -0.51225 2.59289-1.47398 H -1.45347 4.07535-1.24912 H 0.03412 3.82725-0.32431 C 0.97643-3.60280-0.65663 H 0.16740-4.30004-0.89973 H 1.91729-4.16208-0.70698 H 1.00782-2.83184-1.43175 C 0.70907-4.08646 1.80054 H 1.64971-4.64598 1.84909 H 0.52701-3.66499 2.79507 H -0.09070-4.80211 1.58253 C 2.07165 1.69819 3.89326 H 1.35928 0.96378 4.28166 H 3.04078 1.48929 4.36046 H 1.74887 2.69163 4.22297 C 3.17873 2.69125 1.87844 H 2.83616 3.69246 2.15881 H 4.17145 2.55503 2.32005 H 3.29511 2.66976 0.79096 C 4.87139 0.83529-3.42496 N 5.92445 1.05506-3.88645 8.11 Breslow Intermediate E-23 1843.863215 hartree +0.711546 hartree S32

+0.753609 hartree +0.638359 hartree +0.647157 hartree C -1.00171 0.31866 0.08631 C -2.71123 1.85059-0.36723 C -1.44027 2.30338-1.07867 N -0.41132 1.43908-0.49725 H -2.93472 2.48756 0.50251 H -1.19336 3.35171-0.88467 H -3.58938 1.84336-1.01873 H -1.51114 2.16974-2.17083 C -3.25915-0.59256-0.32872 C -4.31367-0.92944 0.54230 C -3.07118-1.27279-1.54909 C -5.18617-1.95416 0.16857 C -3.95656-2.30698-1.86617 C -5.00818-2.64529-1.02344 H -6.00845-2.22186 0.82828 H -3.82159-2.84773-2.80093 H -5.68807-3.44773-1.29569 C 0.85627 1.96788-0.11867 C 1.13902 2.25574 1.23058 C 1.81221 2.18051-1.13388 C 2.43286 2.67697 1.55044 C 3.07780 2.64061-0.76731 C 3.39880 2.85960 0.56764 H 2.67744 2.88984 2.58930 H 3.83127 2.80378-1.53420 H 4.39815 3.18614 0.84074 N -2.39255 0.48391 0.06106 C -0.40791-0.73649 0.72864 O -1.18359-1.51164 1.58655 H -1.92427-0.96965 1.88871 C 0.97142-1.15746 0.65016 C 1.55614-1.87141 1.71513 C 1.76583-0.91398-0.48922 C 2.89149-2.24728 1.67863 H 0.94618-2.11394 2.57905 C 3.09746-1.28418-0.52386 H 1.31257-0.44242-1.35689 C 3.67723-1.93953 0.56779 H 3.32997-2.77561 2.51903 H 3.69988-1.07561-1.40483 C -4.52577-0.20076 1.85467 H -3.61965 0.38936 2.05555 C -1.97456-0.92569-2.53712 H -1.41882-0.06578-2.15645 C 0.08768 2.21375 2.32362 H -0.84964 1.84464 1.89414 C 1.46932 1.94328-2.59227 H 0.58362 1.29141-2.61759 C -4.73325-1.15960 3.02597 H -4.77912-0.60863 3.97043 H -5.67257-1.71435 2.93013 H -3.92681-1.89627 3.10013 C -5.69325 0.78199 1.74840 S33

H -5.82457 1.34081 2.68078 H -5.54468 1.50288 0.93818 H -6.62847 0.24821 1.54414 C -2.54772-0.51613-3.89371 H -3.07223-1.34608-4.37963 H -3.25873 0.31183-3.79877 H -1.74393-0.19703-4.56688 C -0.97398-2.07146-2.68269 H -0.54685-2.35052-1.71421 H -1.45023-2.96151-3.10928 H -0.15026-1.78477-3.34714 C 0.46955 1.27384 3.46432 H -0.33307 1.22256 4.20810 H 1.37224 1.62055 3.97980 H 0.66473 0.26120 3.10053 C -0.18541 3.62577 2.84662 H 0.70837 4.05728 3.31059 H -0.49495 4.30092 2.04144 H -0.97755 3.61236 3.60283 C 1.10356 3.26268-3.27811 H 0.29834 3.78840-2.75563 H 1.96923 3.93447-3.30096 H 0.78400 3.09368-4.31211 C 2.57652 1.23935-3.37160 H 2.24207 1.01770-4.39011 H 3.47463 1.86035-3.45558 H 2.87003 0.29561-2.90278 C 5.11967-2.30465 0.50291 F 5.55643-2.92661 1.61949 F 5.91530-1.21540 0.32414 F 5.39706-3.13168-0.54086 8.12 Breslow Intermediate E-24 4080.365510 hartree +0.696811 hartree +0.736806 hartree +0.624988 hartree +0.634032 hartree C 1.04717 0.32119-0.14944 C 2.78594 1.84573 0.20138 C 1.53499 2.35458 0.91109 N 0.48451 1.48310 0.38525 H 2.99515 2.42883-0.70871 H 1.30340 3.39763 0.67325 H 3.67830 1.86685 0.83289 H 1.62389 2.27011 2.00728 C 3.28277-0.60302 0.33904 C 4.34236-1.01895-0.49192 C 3.06534-1.19934 1.59841 C 5.18987-2.03262-0.03885 C 3.92723-2.22534 1.99625 C 4.98365-2.63873 1.19405 S34

H 6.01476-2.35871-0.66837 H 3.76947-2.69978 2.96295 H 5.64453-3.43321 1.52923 C -0.79030 2.00302 0.02589 C -1.11753 2.23055-1.32475 C -1.71306 2.26447 1.06091 C -2.41983 2.64285-1.62108 C -2.98773 2.71595 0.71591 C -3.35211 2.87527-0.61653 H -2.69853 2.80766-2.66012 H -3.71499 2.91659 1.49922 H -4.35913 3.19320-0.87143 N 2.44425 0.46018-0.13965 C 0.43214-0.75567-0.72610 O 1.18576-1.59882-1.53887 H 1.95143-1.10001-1.85302 C -0.95521-1.15030-0.60988 C -1.57217-1.89185-1.63581 C -1.72247-0.84805 0.52959 C -2.91176-2.24895-1.55922 H -0.98475-2.17887-2.50231 C -3.06378-1.18877 0.61035 H -1.24564-0.35094 1.37033 C -3.65912-1.87605-0.44479 H -3.37760-2.80883-2.36397 H -3.64744-0.93508 1.49025 C 4.58483-0.38191-1.84603 H 3.68865 0.20280-2.09948 C 1.96118-0.77528 2.54768 H 1.41630 0.06038 2.10428 C -0.10136 2.13431-2.44696 H 0.84499 1.77369-2.03024 C -1.32743 2.07665 2.51583 H -0.44816 1.41616 2.53589 C 4.80020-1.41780-2.94781 H 4.86924-0.93078-3.92547 H 5.73043-1.97646-2.79949 H 3.98499-2.14747-2.98753 C 5.76073 0.59468-1.78475 H 5.91324 1.08984-2.74942 H 5.60555 1.36885-1.02651 H 6.68704 0.06728-1.52944 C 2.52245-0.27816 3.87982 H 3.03049-1.07738 4.43051 H 3.24459 0.53304 3.73604 H 1.71394 0.09744 4.51791 C 0.94906-1.90067 2.75821 H 0.52821-2.23797 1.80561 H 1.41273-2.76512 3.24686 H 0.12170-1.56449 3.39461 C -0.52507 1.15243-3.53593 H 0.24785 1.07472-4.30811 H -1.44872 1.47756-4.02794 H -0.70154 0.15414-3.12636 C 0.16484 3.52187-3.03484 H -0.74020 3.94132-3.48821 H 0.50347 4.22636-2.26736 H 0.93317 3.47209-3.81375 C -0.92699 3.41337 3.14613 S35

H -0.13759 3.91559 2.57856 H -1.78616 4.09312 3.17990 H -0.57066 3.27323 4.17259 C -2.41641 1.41096 3.35269 H -2.04982 1.21500 4.36564 H -3.30321 2.04652 3.44826 H -2.73727 0.45764 2.92268 Br -5.48938-2.33838-0.33763 8.13 Breslow Intermediate E-25 1621.294664 hartree +0.739221 hartree +0.780251 hartree +0.667993 hartree +0.675938 hartree C -0.64719-0.14495 0.27640 C -2.16626-1.77821 0.98304 C -0.87272-2.46400 0.55261 N 0.06084-1.34671 0.41413 H -3.06164-2.24315 0.56112 H -0.99827-3.01148-0.39692 H -2.26763-1.77046 2.07960 H -0.49589-3.17085 1.29890 C -2.99752 0.08982-0.45286 C -4.10455 0.77221 0.09237 C -2.87358-0.09954-1.84515 C -5.09063 1.25072-0.77361 C -3.87457 0.41981-2.67112 C -4.97740 1.08348-2.14800 H -5.95245 1.77283-0.36400 H -3.78934 0.28598-3.74793 H -5.74668 1.47006-2.81075 C 1.38629-1.44704 0.92087 C 1.73492-0.86636 2.15587 C 2.33440-2.14860 0.14597 C 3.07199-0.93575 2.55782 C 3.64859-2.22381 0.60947 C 4.02456-1.60015 1.79394 H 3.36345-0.48214 3.50336 H 4.39329-2.75610 0.02203 H 5.05730-1.64360 2.12869 N -2.01675-0.41414 0.46638 C -0.17706 1.12440 0.10735 O -1.03353 2.19178 0.36986 H -1.73719 1.86816 0.94772 C 1.14389 1.54245-0.32504 C 1.65415 2.79182 0.06080 C 1.94339 0.75379-1.17517 C 2.92089 3.21798-0.33071 H 1.04072 3.43790 0.68135 C 3.20633 1.16231-1.56448 H 1.54670-0.18684-1.54901 S36

C 3.71145 2.39484-1.13534 H 3.27875 4.18812-0.00243 H 3.82169 0.54894-2.21667 C -4.25024 0.97868 1.58728 H -3.27645 0.75439 2.04590 C -1.72728-0.85428-2.48984 H -1.06893-1.23134-1.70552 C 0.71540-0.25338 3.09711 H -0.26537-0.27575 2.61124 C 1.93380-2.82822-1.14929 H 0.98364-2.37744-1.47103 C -5.26531-0.00310 2.17537 H -5.34388 0.11323 3.26144 H -6.25998 0.16808 1.74770 H -4.99286-1.04209 1.96416 C -4.62078 2.41666 1.94523 H -3.92426 3.13854 1.50668 H -5.62454 2.67517 1.59129 H -4.61624 2.55586 3.03083 C -0.88352 0.06535-3.37128 H -0.02321-0.47509-3.78407 H -1.46740 0.45279-4.21414 H -0.50450 0.91997-2.80175 C -2.22349-2.07016-3.27242 H -2.82312-2.73722-2.64330 H -2.84355-1.77840-4.12732 H -1.37510-2.64474-3.66248 C 0.60441-1.08752 4.37503 H 1.54956-1.09474 4.92945 H -0.16529-0.67893 5.03864 H 0.34575-2.12908 4.15516 C 1.03048 1.20466 3.42142 H 1.97859 1.29485 3.96400 H 1.11030 1.80594 2.51149 H 0.24806 1.63899 4.05323 C 2.94281-2.62603-2.27642 H 3.15784-1.56689-2.44565 H 3.89384-3.12738-2.06627 H 2.55727-3.04565-3.21148 C 1.69291-4.32356-0.92482 H 1.32954-4.80497-1.83950 H 2.62427-4.82185-0.63164 H 0.96194-4.50814-0.13161 O 4.96830 2.70986-1.56943 C 5.49357 3.95263-1.15450 H 4.88197 4.79033-1.51491 H 5.56865 4.01374-0.06074 H 6.49081 4.02147-1.58902 8.14 Breslow Intermediate E-26 1640.726066 hartree +0.779592 hartree +0.822413 hartree +0.706311 hartree +0.714793 hartree S37

C -0.84729-0.06182 0.30270 C -2.45072 0.79190 1.77637 C -1.17972 1.62767 1.89800 N -0.19470 0.83287 1.16657 H -2.57020 0.12204 2.64243 H -0.85404 1.76024 2.93487 H -3.35752 1.39612 1.68425 H -1.30859 2.62973 1.45417 C -3.16459 0.16283-0.53290 C -4.26816-0.71529-0.55348 C -2.99886 1.14500-1.53192 C -5.20770-0.58921-1.57935 C -3.95336 1.21433-2.55090 C -5.05185 0.36384-2.57806 H -6.06604-1.25696-1.60194 H -3.83535 1.96360-3.33157 H -5.78446 0.44376-3.37643 C 1.11111 0.63412 1.69268 C 1.45459-0.56613 2.34472 C 2.05038 1.67559 1.53222 C 2.77937-0.73135 2.75894 C 3.35042 1.47880 1.99966 C 3.72366 0.27388 2.58514 H 3.06639-1.65807 3.25264 H 4.08772 2.26972 1.87969 H 4.74665 0.12393 2.91978 N -2.23322 0.01984 0.54927 C -0.31822-0.96765-0.56836 O -1.13437-1.98941-1.04880 H -1.88039-2.07972-0.44131 C 1.03870-1.02583-1.07886 C 1.61625-2.25225-1.45029 C 1.83294 0.12014-1.24120 C 2.93055-2.33993-1.88461 H 1.01792-3.15575-1.37727 C 3.14906 0.04531-1.66669 H 1.39959 1.09497-1.02945 C 3.74055-1.19184-1.99036 H 3.32997-3.31679-2.13512 H 3.72196 0.96256-1.75399 C -4.45913-1.77060 0.51829 H -3.50559-1.86547 1.05722 C -1.85587 2.14151-1.54643 H -1.23804 1.98120-0.66137 C 0.43618-1.63462 2.69412 H -0.53255-1.34096 2.27739 C 1.65275 2.98882 0.88627 H 0.73085 2.80137 0.31680 C -4.81141-3.13877-0.06206 H -4.83630-3.89601 0.72785 H -5.79892-3.13525-0.53585 H -4.08772-3.45998-0.81814 C -5.51361-1.32865 1.53473 H -5.62491-2.06770 2.33523 H -5.25721-0.36822 1.99320 S38

H -6.48998-1.21007 1.05066 C -2.36363 3.58175-1.47579 H -2.94089 3.85442-2.36624 H -3.00866 3.73920-0.60431 H -1.52113 4.27979-1.40377 C -0.95152 1.93152-2.75999 H -0.56277 0.90859-2.79079 H -1.49263 2.11665-3.69511 H -0.09655 2.61771-2.72957 C 0.79332-2.99541 2.10225 H 0.01815-3.73364 2.33485 H 1.73837-3.37145 2.51101 H 0.90013-2.94080 1.01537 C 0.26645-1.72462 4.21228 H 1.19727-2.03663 4.69924 H -0.02098-0.75928 4.64327 H -0.50530-2.45683 4.47319 C 1.34314 4.04529 1.95030 H 0.58801 3.70105 2.66354 H 2.24561 4.28803 2.52342 H 0.97901 4.97119 1.49131 C 2.69451 3.52457-0.09201 H 2.31589 4.41889-0.59803 H 3.62215 3.81020 0.41614 H 2.94960 2.78725-0.85901 N 5.06106-1.26668-2.42528 C 5.69178-2.56611-2.46607 C 5.92012-0.13041-2.17796 H 5.96971 0.14650-1.11104 H 5.57902 0.74875-2.73475 H 6.92871-0.36353-2.52257 H 5.17158-3.22889-3.16492 H 5.71771-3.06639-1.48326 H 6.71661-2.45412-2.82352 8.15 Breslow Intermediate E-27 2180.951710 hartree +0.715948 hartree +0.761542 hartree +0.638801 hartree +0.648755 hartree C -1.13413 0.28822 0.40960 C -2.82390 1.30445 1.66332 C -1.57212 2.16275 1.74220 N -0.54546 1.27038 1.19783 H -3.01244 0.76681 2.60556 H -1.30492 2.45398 2.76321 H -3.72047 1.87777 1.41219 H -1.67631 3.08276 1.14463 C -3.43061 0.16414-0.48544 C -3.38197 0.98878-1.62638 C -4.39415-0.85092-0.35017 S39

C -4.32738 0.77327-2.63406 C -5.33071-1.01382-1.37310 C -5.29958-0.21225-2.50942 H -4.30425 1.39863-3.52483 H -6.08619-1.79152-1.28301 H -6.03140-0.35774-3.29931 C 0.82800 1.41669 1.55288 C 1.46616 0.42294 2.32768 C 1.52240 2.55959 1.10448 C 2.82691 0.58417 2.59920 C 2.87010 2.69520 1.44667 C 3.52562 1.70777 2.16870 H 3.35011-0.17815 3.16807 H 3.42099 3.57018 1.10930 H 4.58336 1.80853 2.39491 N -2.50707 0.36530 0.58786 C -0.55188-0.70358-0.35017 O -1.38577-1.77656-0.64966 H -1.35430-1.93958-1.60019 C 0.84613-0.77946-0.71450 C 1.62596-1.96882-0.70316 C 1.49932 0.40262-1.13091 C 2.98371-1.92408-1.02268 C 2.84501 0.44454-1.42696 H 0.89733 1.30398-1.21385 C 3.60312-0.72833-1.36410 H 3.56948-2.83406-0.98061 H 3.31580 1.38089-1.71698 C -2.35609 2.09107-1.80204 H -1.73466 2.12841-0.90261 C -4.42310-1.75035 0.86646 H -3.49674-1.56687 1.42402 C 0.69032-0.75224 2.89165 H 0.03733-1.13848 2.10024 C 0.85500 3.62115 0.24947 H -0.06730 3.18489-0.15770 C -1.42265 1.79727-2.97584 H -1.97037 1.78443-3.92488 H -0.64043 2.56155-3.05456 H -0.93268 0.82444-2.85845 C -3.00780 3.46530-1.94855 H -3.60746 3.53252-2.86288 H -3.66851 3.69140-1.10497 H -2.24287 4.24951-1.99866 C -4.44240-3.22785 0.48388 H -4.40267-3.85511 1.38000 H -5.35675-3.49414-0.05856 H -3.58541-3.48364-0.14456 C -5.60851-1.40478 1.76903 H -6.55888-1.58108 1.25138 H -5.60503-2.02148 2.67382 H -5.59516-0.35351 2.07617 C 1.57255-1.90712 3.34900 H 2.15731-1.64541 4.23830 H 0.95297-2.76954 3.60903 H 2.26989-2.22617 2.56810 C -0.20721-0.29381 4.04514 H 0.39467 0.08140 4.88073 H -0.88901 0.50667 3.74224 S40

H -0.81449-1.12631 4.41565 C 0.48186 4.84665 1.08771 H -0.11570 4.58180 1.96497 H 1.38608 5.34797 1.45118 H -0.08595 5.57165 0.49409 C 1.70147 4.05320-0.94696 H 1.14053 4.75701-1.57092 H 2.62067 4.56010-0.63615 H 1.98757 3.20596-1.57771 C 1.06354-3.30976-0.31951 C 5.06546-0.66100-1.64554 F 0.30201-3.27657 0.79205 F 2.04781-4.20916-0.06969 F 0.30868-3.86189-1.30851 F 5.71632 0.11687-0.73946 F 5.66141-1.87068-1.62327 F 5.32814-0.10938-2.85826 8.16 Breslow Intermediate E-28 1504.561039 hartree +0.676351 hartree +0.713843 hartree +0.610747 hartree +0.616133 hartree C 0.30556 0.06116-0.10648 C 1.19268-0.02225-2.25121 C -0.27827 0.30300-2.35036 N -0.75896-0.01162-1.00512 H 1.38646-1.08374-2.47830 H -0.80615-0.29300-3.10311 H 1.82056 0.58374-2.91003 H -0.44346 1.36973-2.58055 C 2.75589-0.15701-0.35799 C 2.98742-1.51930-0.08675 C 3.76237 0.81308-0.19115 C 4.25224-1.89219 0.38143 C 5.01125 0.38463 0.26640 C 5.25919-0.95280 0.55789 H 4.44627-2.93958 0.60584 H 5.79679 1.12445 0.40735 H 6.23640-1.26072 0.91975 C -2.08578 0.42032-0.68792 C -3.14037-0.47514-0.94799 C -2.32237 1.70910-0.17279 C -4.43940-0.07870-0.62802 C -3.63786 2.04796 0.15979 C -4.68814 1.16388-0.05497 H -5.26642-0.76023-0.81796 H -3.83980 3.03338 0.57542 H -5.70277 1.44963 0.20892 N 1.47645 0.27629-0.84418 C 0.24521-0.02574 1.25924 S41

O 1.36190 0.40476 1.98027 H 1.68087-0.33051 2.52139 C 1.93352-2.59951-0.26865 H 1.01482-2.14570-0.65332 C 3.55561 2.30265-0.41259 H 4.55393 2.74579-0.28584 C -2.89651-1.82712-1.58771 H -1.81114-1.98428-1.61725 C -1.23375 2.75601-0.02641 H -0.28359 2.32094-0.35400 C 1.56933-3.26059 1.06079 H 0.78446-4.01042 0.91610 H 2.43465-3.76391 1.50709 H 1.18921-2.53084 1.78293 C 2.38872-3.64790-1.28463 H 2.63957-3.19368-2.24909 H 3.27831-4.18375-0.93541 H 1.60208-4.39072-1.45280 C 2.64699 2.92663 0.64645 H 2.59485 4.01279 0.50577 H 1.63325 2.52406 0.57542 H 2.99998 2.72370 1.66085 C 3.07742 2.70206-1.80964 H 3.61078 2.16498-2.60114 H 2.00389 2.52162-1.92821 H 3.24293 3.77303-1.96647 C -3.50270-2.97969-0.79117 H -4.58844-2.87273-0.68546 H -3.31896-3.93275-1.29803 H -3.06669-3.04241 0.20854 C -3.42724-1.83601-3.02332 H -4.51699-1.71594-3.03638 H -3.00597-1.01984-3.61989 H -3.19201-2.78095-3.52458 C -1.50669 3.95595-0.93541 H -1.63299 3.65408-1.98059 H -2.41625 4.48830-0.63486 H -0.67437 4.66726-0.88531 C -1.05757 3.20792 1.42209 H -0.25921 3.95379 1.49816 H -1.97680 3.66589 1.80541 H -0.80226 2.36933 2.07586 C -0.86428-0.42259 2.07650 C -1.14751-0.15743 3.39780 O -1.79945-1.29404 1.57876 C -2.33384-0.87716 3.71351 H -0.58424 0.50841 4.03580 C -2.69712-1.53825 2.58138 H -2.86111-0.89204 4.65666 H -3.52643-2.17548 2.31547 8.17 Breslow Intermediate E-29 1584.176952 hartree +0.740347 hartree +0.780805 hartree S42

+0.669692 hartree +0.677843 hartree O -1.01045 1.31539-1.38661 N -0.16525-1.38957 0.96333 N -2.15918-0.57607 0.32230 C -0.17168 0.58109-0.55278 C -0.78561-0.39346 0.20972 C -1.16221-2.38166 1.36565 C -2.43485-1.56672 1.36129 C -3.10990 0.48657 0.18058 C -4.10129 0.32874-0.80512 C -4.11222-0.91015-1.68181 C -5.47157-1.19483-2.30898 C -3.03185-0.83739-2.76422 C -5.03409 1.35427-0.96371 C -4.98271 2.49668-0.16827 C -4.01280 2.61511 0.81842 C -3.06461 1.60705 1.02509 C -2.04409 1.76542 2.13781 C -1.09313 2.93284 1.87133 C -2.72645 1.93160 3.49631 C 1.15548-1.87118 0.69499 C 2.10544-1.74165 1.72769 C 1.71011-1.11184 3.05192 C 2.63397-1.49358 4.20187 C 1.61218 0.41219 2.93477 C 3.41147-2.16426 1.47290 C 3.76048-2.69406 0.23273 C 2.80038-2.83656-0.76021 C 1.47481-2.44146-0.54970 C 0.45465-2.64746-1.65377 C 0.28746-4.13523-1.96787 C 0.81932-1.86716-2.91673 C 1.21847 0.87658-0.57830 C 1.81438 1.81034-1.37190 C 3.22755 2.13612-1.36541 C 4.17475 1.46158-0.56619 C 5.51830 1.80830-0.59913 C 5.97032 2.83660-1.42951 C 5.05104 3.51140-2.23163 C 3.70496 3.16542-2.19957 H -0.82084 2.25461-1.25656 H -0.91381-2.80418 2.34493 H -1.20705-3.20885 0.63694 H -3.32912-2.14868 1.11429 H -2.60544-1.07506 2.33421 H -3.85965-1.76487-1.03736 H -6.27402-1.21623-1.56480 H -5.45659-2.16272-2.81871 H -5.73400-0.44337-3.06207 H -3.22054 0.00227-3.44252 H -3.02457-1.75835-3.35913 H -2.03681-0.69086-2.33915 H -5.80856 1.26594-1.72026 H -5.71064 3.29049-0.31250 H -3.99022 3.50272 1.44820 S43