Supplementary Data 1: A Guide to Small Molecule Structure Assignment Through Computation of ( 1 H and 13 C) NMR Chemical Shifts

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1 pge 1 of 21 Supplementry Dt 1: A Guide to Smll Molecule Structure Assignment Through Computtion of ( 1 H nd 13 C) Chemicl Ptrick H. Willoughy, Mtthew J. Jnsm, nd Thoms R. Hoye Deprtment of Chemistry University of Minnesot Minnepolis, Minnesot, USA Correspondence should e ddressed to T.R.H. (hoye@umn.edu). Contents of Supplementry Dt Tulted experimentl 1 H nd 13 C chemicl shifts for cis- nd trns-3- methylcyclohexnol (1-cis nd 1-trns, respectively) in CDCl 3. Tulted 1 H nd 13 C chemicl shifts for cis- nd trns-3-methylcyclohexnol in CDCl 3 computed with ACD/Ls 1 H Predictor (cf. Figure 2 in the protocol). Tulted 1 H nd 13 C chemicl shifts for 1-cis nd 1-trns in CDCl 3 computed with B3LYP/6-311+G(2d,p)//M06-2X/6-31+G(d,p). Pge Full Cittion for Gussin 09 5 Anticipted Results for 1-trns 6 Totl electronic energy ( SCF Done ) from the opt_freq [E(RM062X)] clcultion, free energy ( Sum of electronic nd therml Free Energies ) from opt_freq, Crtesin coordintes from the opt_freq clcultion, isotropic shielding tensors from the nmr clcultion, nd scled chemicl shifts for the six conformers of 1-cis, 1- trns, nd methylcyclohexne computed with B3LYP/6-311+G(2d,p)//M06-2X/6-31+G(d,p). 7

2 pge 2 of 21 Tulted experimentl 1 H chemicl shifts for cis- nd trns-3-methylcyclohexnol in CDCl 3. cis-3-methylcyclohexnol (1-cis) 1 H (500 MHz, CDCl 3 ) Chemicl Shift (δ) (ppm) trns-3-methylcyclohexnol (1-trns) 1 H (500 MHz, CDCl 3 ) Chemicl Shift (δ) (ppm) CH CH H1xil 3.56 H1 equtoril 4.05 H2 xil 0.88 H2 xil 1.23 H2 equtoril 1.94 H2 equtoril 1.69 H3 xil 1.42 H3 xil 1.83 H4 xil 0.76 H4 xil 0.96 H4 equtoril 1.59 H4 equtoril 1.63 H5 xil 1.26 H5 xil 1.61 H5 equtoril 1.74 H5 equtoril 1.51 H6 xil 1.15 H6 xil 1.49 H6 equtoril 1.94 H6 equtoril 1.63 cis-3-methylcyclohexnol (S-1) 13 C (500 MHz, CDCl 3 ) trns-3-methylcyclohexnol (S-2) 13 C (500 MHz, CDCl 3 ) Chemicl Shift (δ) (ppm) Chemicl Shift (δ) (ppm) CH CH C C C C C C C C C C C C6 33.2

3 pge 3 of 21 Tulted 1 H chemicl shifts for cis- nd trns-3-methylcyclohexnol in CDCl 3 computed with ACD/Ls 1 H Predictor. 1 cis-3-methylcyclohexnol (1-cis) 1 H (Computed with ACD Ls) Chemicl Shift (δ) (ppm) trns-3-methylcyclohexnol (1-trns) 1 H (Computed with ACD Ls) Chemicl Shift (δ) (ppm) CH CH H-1xil 3.52 H1 equtoril 3.81 H2 xil 1.27 H2 xil 1.27 H2 equtoril 1.59 H2 equtoril 1.58 H3 xil 1.57 H3 xil 1.57 H4 xil 1.35 H4 xil 0.88 H4 equtoril 1.30 H4 equtoril 1.64 H5 xil 1.36 H5 xil 1.37 H5 equtoril 1.42 H5 equtoril 1.42 H6 xil 1.66 H6 xil 1.66 H6 equtoril 1.83 H6 equtoril ACD/Ls C+H Predictors nd DB, version 11.0, Advnced Chemistry Development, Inc., Toronto, On, Cnd, (2013).

4 pge 4 of 21 Tulted 1 H nd 13 C chemicl shifts for cis- nd trns-3-methylcyclohexnol in CDCl 3 computed with B3LYP/6-311+G(2d,p)//M06-2X/6-31+G(d,p). cis-3-methylcyclohexnol (1-cis) 1 H (CDCl 3 ) trns-3-methylcyclohexnol (1-trns) 1 H (CDCl 3 ) Chemicl Shift (δ) (ppm) Chemicl Shift (δ) (ppm) CH CH H-1xil 3.44 H1 equtoril 3.96 H2 xil 0.80 H2 xil 1.18 H2 equtoril 1.84 H2 equtoril 1.66 H3 xil 1.39 H3 xil 1.82 H4 xil 0.80 H4 xil 0.95 H4 equtoril 1.55 H4 equtoril 1.62 H5 xil 1.30 H5 xil 1.73 H5 equtoril 1.71 H5 equtoril 1.44 H6 xil 1.05 H6 xil 1.45 H6 equtoril 1.84 H6 equtoril 1.62 cis-3-methylcyclohexnol (1-cis) 13 C (CDCl 3 ) trns-3-methylcyclohexnol (1-trns) 13 C (CDCl 3 ) Chemicl Shift (δ) (ppm) Chemicl Shift (δ) (ppm) CH CH C C C C C C C C C C C C6 33.7

5 pge 5 of 21 Full Cittion for Gussin 09 (ref 33 of mnuscript): Gussin 09, Revision A, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseri, G. E.; Ro, M. A.; Cheesemn, J. R.; Sclmni, G.; Brone, V.; Mennucci, B.; Petersson, G. A.; Nktsuji, H.; Cricto, M.; Li, X.; Hrtchin, H. P.; Izmylov, A. F.; Bloino, J.; Zheng, G.; Sonnenerg, J. L.; Hd, M.; Ehr, M.; Toyot, K.; Fukud, R.; Hsegw, J.; Ishid, M.; Nkjim, T.; Hond, Y.; Kito, O.; Nki, H.; Vreven, T.; Montgomery, J. A., Jr.; Perlt, J. E.; Ogliro, F.; Berprk, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Stroverov, V. N.; Koyshi, R.; Normnd, J.; Rghvchri, K.; Rendell, A.; Burnt, J. C.; Iyengr, S. S.; Tomsi, J.; Cossi, M.; Reg, N.; Millm, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bkken, V.; Admo, C.; Jrmillo, J.; Gomperts, R.; Strtmnn, R. E.; Yzyev, O.; Austin, A. J.; Cmmi, R.; Pomelli, C.; Ochterski, J. W.; Mrtin, R. L.; Morokum, K.; Zkrzewski, V. G.; Voth, G. A.; Slvdor, P.; Dnnenerg, J. J.; Dpprich, S.; Dniels, A. D.; Frks, Ö.; Foresmn, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gussin, Inc., Wllingford CT, 2009.

6 pge 6 of 21 Anticipted Results for 1-trns The expected outcomes following the conformtionl nlysis, geometry optimiztions, nd frequency clcultions for 1-trns re shown in Figure S1. Six conformers re otined from the conformtionl serch with 98.1% of the contriution coming from the three methyl equtoril conformers, which re C OH rotmers of one nother. The computed vlues (referenced nd scled) from the chemicl shift clcultions nd their comprisons with the experimentl vlues for 1-cis re shown in Figure S2, Pnels A nd B. H O CH 3 H O CH 3 O H CH 3 H O CH 3 H O CH 3 O H CH 3 ) ) % 39.0% 11.0% 3.98% % Figure S1 Energies nd Boltzmnn distriution of conformers of 1-trns tht re within 5 kcl mol -1 of the glol minimum. ) The reltive Gis (or free) energy of ech conformer with respect to the glol minimum. ) The Boltzmnn mole frction (in %) for ech conformer. HO CH 3 1 H Chemicl Shift Dt 13 C Chemicl Shift Dt MAE of exp vs. DFT 1 H dt (s) δ DFT (ppm) δ exp (ppm) Asolute Error δ DFT (ppm) δ exp (ppm) Asolute Error 1-cis DFT 1-trns DFT CH 3 1 x 2 x 2 eq 3 x 4 x 4 eq 5 x 5 eq 6 x 6 eq cis exp 1-trns exp c MAE of exp vs. DFT 13 C dt 1-cis DFT 1-trns DFT 1-cis exp MAE = 0.04 MAE = trns exp Figure S2 Comprison of computed nd experimentl dt for 1-cis vs. 1-trns. () Computed [with B3LYP/6-311+G(2d,p)//M06-2X/6-31+G(d,p)] nd experimentl 1 H nd 13 C chemicl shift vlues of 1-trns. ( nd c) MAEs for the 1 H nd 13 C chemicl shifts, respectively, etween mtched nd mismtched pirs of 1-cis vs. 1-trns. Chemicl shifts were derived from ppliction of scling fctors (slope = , intercept = ) to the 1 H shielding tensors computed t the B3LYP/6-311+G(2d,p)//M06-2X/6-31+G(d,p) level of theory. Chemicl shifts were derived from ppliction of scling fctors (slope = , intercept = ) to the 13 C shielding tensors computed t the B3LYP/6-311+G(2d,p)//M06-2X/6-31+G(d,p) level of theory.

7 pge 7 of 21 Totl electronic energy ( SCF Done ) from the opt_freq [E(RM062X)] clcultion, free energy ( Sum of electronic nd therml Free Energies ) from opt_freq, Crtesin coordintes from the opt_freq clcultion, isotropic shielding tensors from the nmr clcultion, nd scled chemicl shifts for the six conformers of 1-cis, 1-trns, nd methylcyclohexne computed with B3LYP/6-311+G(2d,p)//M06-2X/6-31+G(d,p).

8 pge 8 of 21 cis-3-methylcyclohexnol conf-1 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

9 pge 9 of 21 cis-3-methylcyclohexnol conf-2 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

10 pge 10 of 21 cis-3-methylcyclohexnol conf-3 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

11 pge 11 of 21 cis-3-methylcyclohexnol conf-4 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

12 pge 12 of 21 cis-3-methylcyclohexnol conf-5 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

13 pge 13 of 21 cis-3-methylcyclohexnol conf-6 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

14 pge 14 of 21 trns-3-methylcyclohexnol conf-1 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

15 pge 15 of 21 trns-3-methylcyclohexnol conf-2 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

16 pge 16 of 21 trns-3-methylcyclohexnol conf-3 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

17 pge 17 of 21 trns-3-methylcyclohexnol conf-4 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

18 pge 18 of 21 trns-3-methylcyclohexnol conf-5 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

19 pge 19 of 21 trns-3-methylcyclohexnol conf-6 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C O H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

20 pge 20 of 21 methylcyclohexne conf-1 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

pge 21 of 21 methylcyclohexne conf-2 SCF Done: E(RM062X) = -275.064923178 A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = -274.895889 A.U. Crtesin Coordintes (x,y,z) Scled 1 C 1.

21 pge 21 of 21 methylcyclohexne conf-2 SCF Done: E(RM062X) = A.U. (ic Units = Hrtrees) Sum of electronic nd therml Free Energies = A.U. Crtesin Coordintes (x,y,z) Scled 1 C C C C C C C H H H H H H H H H H H H H H The totl electronic energy from nmr clcultion: SCF Done: E(RB3LYP) = A.U. (This vlue is not otherwise used, ut is provided here s dditionl vlue ginst which users cn vlidte their results.) This is the free energy used in the Boltzmnn weighting.

Supporting Information. Why is there no in-plane proton-coupled electron transfer from. A theoretical and experimental investigation

Supporting Information. Why is there no in-plane proton-coupled electron transfer from. A theoretical and experimental investigation Electronic Supplementry Mteril (ESI) for Photochemicl & Photobiologicl Sciences This journl is (c) The Royl Society of Chemistry nd wner Societies 2010 Supporting Informtion Why is there no in-plne proton-coupled