Electronic Supplementary Information

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1 Electronic Supplementary Information The preferred all-gauche conformations in 3-fluoro-1,2-propanediol Laize A. F. Andrade, a Josué M. Silla, a Claudimar J. Duarte, b Roberto Rittner, b Matheus P. Freitas*,a a Department of Chemistry, Federal University of Lavras, P.O. Box 3037, , Lavras, MG, Brazil b Chemistry Institute, State University of Campinas, P.O. Box 6154, , Campinas, SP, Brazil * Corresponding author: matheus@dqi.ufla.br; Tel: ; Fax: Page S1. Figure S1. 1 H NMR spectrum for 3-fluoro-1,2-propanediol acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. Page S2. Figure S2. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H1a and H1b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. Page S3. Figure S3. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H2, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. Page S4. Figure S4. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H3a and H3b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. Page S5. Figure S5. 1 H NMR spectrum for 3-fluoro-1,2-propanediol acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. Page S6. Figure S6. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H1a and H1b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. Page S7. Figure S7. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H2, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. Page S8. Figure S8. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H3a and H3b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. Page S9. Figure S9. 1 H x 19 F HETCOR for 3-fluoro-1,2-propanediol in CDCl 3, at MHz for 1 H and MHz for 19 F, acquired in a Bruker Avance 500 spectrometer using ca. 20 mg ml -1 in CDCl 3 at 298K. Page S10. Optimized geometries for the 25 main conformers of compound 2 obtained at the B3LYP/ g(d,p) level. Page S19. Table S1. Conformers of 2 found at the B3LYP/ g(d,p) level, with respective relative energies (in kcal mol -1 ) and population (%) in the gas phase and solution (CHCl 3 and CH 3 CN implicit solvents). Page S27. Table S2. Calculated and experimental chemical shifts (in ppm, relative to TMS, using the calculated isotropic magnetic shielding tensor) and coupling constants (in Hz) for 2, in CHCl 3. Page S28. Table S2. Calculated and experimental chemical shifts (in ppm, relative to TMS, using the calculated isotropic magnetic shielding tensor) and coupling constants (in Hz) for 2, in CH 3 CN.

2 Figure S1. 1 H NMR spectrum for 3-fluoro-1,2-propanediol acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. 1

3 Figure S2. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H1a and H1b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. 2

4 Figure S3. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H2, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. 3

5 Figure S4. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H3a and H3b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CDCl 3 at 298K. 4

6 Figure S5. 1 H NMR spectrum for 3-fluoro-1,2-propanediol acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. 5

7 Figure S6. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H1a and H1b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. 6

8 Figure S7. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H2, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. 7

9 Figure S8. Expansion of the 1 H NMR spectrum for 3-fluoro-1,2-propanediol in the region of H3a and H3b, acquired in a Bruker Avance III 600 spectrometer operating at MHz, using ca. 20 mg ml -1 in CD 3 CN at 298K. 8

10 Figure S9. 1 H x 19 F HETCOR for 3-fluoro-1,2-propanediol in CDCl 3, at MHz for 1 H and MHz for 19 F, acquired in a Bruker Avance 500 spectrometer using ca. 20 mg ml -1 in CDCl 3 at 298K. 9

11 Optimized geometries for the 25 main conformers of compound 2 obtained at the B3LYP/ g(d,p) level. 2a Standard orientation: Rotational constants (GHZ): b Standard orientation: Rotational constants (GHZ): c Standard orientation: Rotational constants (GHZ):

12 2d Standard orientation: Rotational constants (GHZ): e Standard orientation: Rotational constants (GHZ): f Standard orientation: Rotational constants (GHZ):

13 2g Standard orientation: Rotational constants (GHZ): h Standard orientation: Rotational constants (GHZ): i Standard orientation: Rotational constants (GHZ):

14 2j Standard orientation: Rotational constants (GHZ): k Standard orientation: Rotational constants (GHZ): l Standard orientation: Rotational constants (GHZ):

15 2m Standard orientation: Rotational constants (GHZ): n Standard orientation: Rotational constants (GHZ): o Standard orientation: Rotational constants (GHZ):

16 2p Standard orientation: Rotational constants (GHZ): q Standard orientation: Rotational constants (GHZ): r Standard orientation: Rotational constants (GHZ):

17 2s Standard orientation: Rotational constants (GHZ): t Standard orientation: Rotational constants (GHZ): u Standard orientation: Rotational constants (GHZ):

18 2v Standard orientation: Rotational constants (GHZ): w Standard orientation: Rotational constants (GHZ): x Standard orientation: Rotational constants (GHZ):

19 2y Standard orientation: Rotational constants (GHZ):

20 Table S1. Conformers of 2 found at the B3LYP/ g(d,p) level, with respective relative energies (in kcal mol -1 ) and population (%) in the gas phase and solution (CHCl 3 and CH 3 CN implicit solvents). Structure Conformer E gas % gas E CHCl3 % CHCl3 E CH3CN % CH3CN 2a b c d e f g

21 2h i j k l m n o

22 2p q r s t u v w

23 2x y z aa ab ac ad

24 2ae af ag ah ai aj ak

25 2al am an ao ap aq ar

26 2as at au av aw ax ay

27 2az ba

28 Table S2. Calculated and experimental chemical shifts (in ppm, relative to TMS, using the calculated isotropic magnetic shielding tensor) and coupling constants (in Hz) for 2, in CHCl 3. Conformer δ H1a δ H1b δ H2 δ H3a δ H3b 2 J H1a,H1b 3 J H1a,H2 4 J H1a,F 3 J H1b,H2 4 J H1b,F 3 J H2,H3a 3 J H2,H3b 3 J H2,F 2 J H3a,H3b 2 J H3a,F 2a b c d e f g h i j k l m n o p q r s t u v w x y Exp. CDCl J H3b,F 27

29 Table S3. Calculated and experimental chemical shifts (in ppm, relative to TMS, using the calculated isotropic magnetic shielding tensor) and coupling constants (in Hz) for 2, in CH 3 CN. Conformer δ H1a δ H1b δ H2 δ H3a δ H3b 2 J H1a,H1b 3 J H1a,H2 4 J H1a,F 3 J H1b,H2 4 J H1b,F 3 J H2,H3a 3 J H2,H3b 3 J H2,F 2 J H3a,H3b 2 J H3a,F 2a b c d e f g h i j k l m n o p q r s t u v w x y Exp. CH3CN J H3b,F 28