Keto-Enol Thermodynamics of Breslow Intermediates
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1 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
2 1 Computational Details The conformational space of each structure was explored a modified Monte Carlo search routine implemented in MacroModel 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 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 S2
3 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 ΔΔG KE = 5.09σ P r 2 = 0.94 X = NMe X = H X = OMe σ p X = CN X = Br X = CF ΔG 4.0 Breslow = 5.99σ P 8.27 ΔG r 2 = 0.95 Breslow X = NMe X = H X = OMe X = Br X = CF 3 X = CN σ p Dipp N + N Dipp 6.0 H O X G Ketone Dipp N O N Dipp X Dipp N r OH N Dipp X ΔG Ketone X = NMe 2 ΔG Ketone = 0.90σ P 7.15 r 2 = 0.90 X = OMe r r =0.0064σ P r 2 = 0.80 X = H X = CN X = CF X = H X = Br X = CF X = NMe 2 X = OMe X = Br X = CN σ p 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
4 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
5 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
6 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
7 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
8 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 Toluene THF Dichloroethane Benzaldehyde Acetonitrile Water S8
9 6 Coordinates and Calculated Energies for Free Carbenes 6.1 Carbene C hartree hartree hartree hartree hartree N N C N C C C C C C C C H H H H H C C C C C H H H H H C C C C C C H H H H H Carbene C hartree hartree hartree S9
10 hartree hartree C N C H H N H H C C C C C C C C C H C H C C C C C C H H C H C C C C H H C C C H C H H H H H H H H H H H H H S10
11 H H H H H H H H H H H H H Carbene C hartree hartree hartree hartree hartree C N C H H N H H C C C C C C C H H H H H C C C C C H H H H H C S11
12 6.4 Carbene C hartree hartree hartree hartree hartree C N C H H N H H C C C C C C C C C H C H C C C C C C C H C H C H H H H H H H H H H H H H H H S12
13 H H H Carbene C hartree hartree hartree hartree hartree C N C N C C C C C C C C C H C H C C C C C C H H C H C C C C H H C C C H C H H H H H S13
14 H H H H H H H H H H H H H H H H H H H H H H H Carbene C hartree hartree hartree hartree hartree C N C N C C C C C C C H H H H H C C C C C H S14
15 H H H H C H H Carbene C hartree hartree hartree hartree hartree C N C S C C C C C C H H H H H C H H S15
16 7 Coordinates and Calculated Energies for Free Aldehydes 7.1 Aldehyde A hartree hartree hartree hartree hartree C C C C C C H H H H H C O H Aldehyde A hartree hartree hartree hartree hartree C C C C C C H H H C H C O H N S16
17 7.3 Aldehyde A hartree hartree hartree hartree hartree C C C C C C H H H C H C O H F F F Aldehyde A hartree hartree hartree hartree hartree C C C C C C H H H Br H C O H S17
18 7.5 Aldehyde A hartree hartree hartree hartree hartree C C C C C C H H H O H C O H C H H H Aldehyde A hartree hartree hartree hartree hartree C C C C C C H H H N H C O H C H H S18
19 H C H H H Aldehyde A hartree hartree hartree hartree hartree C C C C C C H H H C C C O H F F F F F F Aldehyde A hartree hartree hartree hartree hartree C O C C C C H S19
20 H O H H Aldehyde A hartree hartree hartree hartree hartree C C C C C C H C H H H H C H H C O H S20
21 8 Coordinates and Calculated Energies for Breslow Intermediates 8.1 Breslow Intermediate E-E hartree hartree hartree hartree hartree C N N N C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H C C O H C C C C H S21
22 C H C H H H Breslow Intermediate Z-E hartree hartree hartree hartree hartree C N N N C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H C C S22
23 O H C C C C H C H C H H H Breslow Intermediate E hartree hartree hartree hartree hartree O N N C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S23
24 C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H Breslow Intermediate E hartree hartree hartree hartree S24
25 hartree C C C N H H H H C C C C C C H H H C C C C C C H H H N C O H C C C C H C H C H H H H H H H Breslow Intermediate E hartree hartree hartree hartree S25
26 hartree C C C N H H H H C C C C C C H H C C C C C C H H N C O H C C C C H C H C H H H C H C H C H C H H H H H H H H H S26
27 C H H H C H H H Breslow Intermediate E hartree hartree hartree hartree hartree C C N N C H H C O C C C C C C H H H H H C C C C C C C C H H H C C C C C C S27
28 C H H C H C H H H C H C H H H H H H C H H H H H C C H H H H H H C H C H H H H H H H Breslow Intermediate E hartree hartree hartree hartree hartree C C N S28
29 N C H H C O C C C C C C H H H H H C C C C C C H H H H H C C C C C C H H H H H H Breslow Intermediate E-E hartree hartree hartree hartree hartree C C S N C S29
30 H H C O C C C C C C H H H H H C C C C C C H H H H H H Breslow Intermediate Z-E hartree hartree hartree hartree hartree C C S N C H H C O C C C C C C H H H S30
31 H H C C C C C C H H H H H H Breslow Intermediate E hartree hartree hartree hartree hartree C C C N H H H H C C C C C C H H H C C C C C C H H H N C O H C S31
32 C C C H C H C H H C H C H C H C H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C N Breslow Intermediate E hartree hartree S32
33 hartree hartree hartree C C C N H H H H C C C C C C H H H C C C C C C H H H N C O H C C C C H C H C H H C H C H C H C H C H H H C S33
34 H H H C H H H C H H H C H H H C H H H C H H H C H H H C F F F Breslow Intermediate E hartree hartree hartree hartree hartree C C C N H H H H C C C C C C S34
35 H H H C C C C C C H H H N C O H C C C C H C H C H H C H C H C H C H C H H H C H H H C H H H C H H H C H H H C H H H C S35
36 H H H C H H H Br Breslow Intermediate E hartree hartree hartree hartree hartree C C C N H H H H C C C C C C H H H C C C C C C H H H N C O H C C C C H C H S36
37 C H H C H C H C H C H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H O C H H H Breslow Intermediate E hartree hartree hartree hartree hartree S37
38 C C C N H H H H C C C C C C H H H C C C C C C H H H N C O H C C C C H C H C H H C H C H C H C H C H H H C H H S38
39 H C H H H C H H H C H H H C H H H C H H H C H H H N C C H H H H H H Breslow Intermediate E hartree hartree hartree hartree hartree C C C N H H H H C C C S39
40 C C C H H H C C C C C C H H H N C O H C C C C C H C H H C H C H C H C H C H H H C H H H C H H H C H H H C H H H C H H S40
41 H C H H H C H H H C C F F F F F F Breslow Intermediate E hartree hartree hartree hartree hartree C C C N H H H H C C C C C C H H H C C C C C C H H H N C S41
42 O H C H C H C H C H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C C O C H C H H Breslow Intermediate E hartree hartree hartree S42
43 hartree hartree O N N C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H S43
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