Science Advances

Supplementary Materials

This PDF file includes:

  • General information
  • Synthetic procedures
  • Enantioselective sensing experiments
  • Quantitative ee and concentration analysis
  • Ee and concentration analysis of hydrobenzoin 25 obtained by asymmetric Sharpless dihydroxylation
  • MS analysis of the in situ complex formation
  • Analysis of the sensing mechanism with the stereodynamic Ti complex
  • Crystallography
  • Scheme S1. General synthesis of 1.
  • Fig. S1. 1H and 13C NMR spectra of 2 in CDCl3.
  • Fig. S2. 1H and 13C NMR spectra of 3 in CDCl3.
  • Fig. S3. 1H and 13C NMR spectra of 1 in CDCl3.
  • Fig. S4. Structures of substrates 4 to 29.
  • Fig. S5. CD response of the zinc complex of 1 to chiral diamines, amines, and amino alcohols.
  • Fig. S6. CD response of the zinc complex of 1 to chiral amino acids.
  • Fig. S7. CD response of the aluminum complex of 1 to carboxylic acids.
  • Fig. S8. CD response of the titanium complex of 1 to chiral diols.
  • Fig. S9. CD spectra obtained from 1, (S)-19, and Me3Al (solid red) and from 1, (S)-19, and B(OMe)3 (dashed red).
  • Fig. S10. CD spectra of the Zn complex obtained with 1 and scalemic samples of 14.
  • Fig. S11. Exponential relationship between the CD amplitudes at 338 nm (blue), 385 nm (red), and 445 nm (green) and the ee of 14.
  • Fig. S12. Fluorescence spectra of the complexes formed from 1, Et2Zn, and varying concentrations of 14 from 0 to 100 mol% (blue) and 120 to 200 mol% (red).
  • Fig. S13. Fluorescence intensity (I) measured at 600 nm plotted against the ratio of 14/1.
  • Fig. S14. Curve fitting of the fluorescence emission at 600 nm.
  • Fig. S15. CD spectra of the Ti complex obtained with 1 and scalemic samples of 25.
  • Fig. S16. Linear relationship between the CD amplitudes at 375 nm (red) and 470 nm (blue) and the ee of 25.
  • Fig. S17. Fluorescence spectra of the complexes formed from 1, Ti(Oi-Pr)4, and varying concentrations of 25 from 0 to 100 mol% (blue) and 120 to 160 mol% (red).
  • Fig. S18. Fluorescence intensity (I) measured at 585 nm plotted against the ratio of 25/1.
  • Fig. S19. Curve fitting of the fluorescence emission at 585 nm.
  • Fig. S20. Asymmetric Sharpless dihydroxylation of trans-stilbene.
  • Fig. S21. HPLC separation of the product obtained with AD-mix-β at 0°C on a Chiralcel OJ column using hexanes/i-PrOH (92:8, v/v) as mobile phase.
  • Fig. S22. HPLC separation of the product obtained with AD-mix-β at 25°C on a Chiralcel OJ column using hexanes/i-PrOH (92:8, v/v) as mobile phase.
  • Fig. S23. HPLC separation of the product obtained with AD-mix-β at 50°C on a Chiralcel OJ column using hexanes/i-PrOH (92:8, v/v) as mobile phase.
  • Fig. S24. HPLC separation of the product obtained with cinchonine at 25°C on a Chiralcel OJ column using hexanes/i-PrOH (92:8, v/v) as mobile phase.
  • Fig. S25. MS spectrum of the complex obtained from 1, Et2Zn, and (1R,2R)-4.
  • Fig. S26. MS spectrum of the complex obtained from 1, Et2Zn, and (1R,2S)-10.
  • Fig. S27. MS spectrum of the complex obtained from 1, Et2Zn, and (1R,2S)-14.
  • Fig. S28. MS spectrum of the complex obtained from 1, Me3Al, and (R)-23.
  • Fig. S29. MS spectrum of the complex obtained from 1, Ti(Oi-Pr)4, and (1R,2R)-25.
  • Fig. S30. MS spectrum of the complexes obtained from 1, Ti(Oi-Pr)4, and a mixture of (1S,2S)-25 and (2R,3R)-26.
  • Fig. S31. MS spectrum of the complexes obtained from 1, Ti(Oi-Pr)4, (1S,2S)-25, and (2S,3S)-26.
  • Fig. S32. Excerpt of the NMR spectrum showing the methine proton septet in Ti(Oi-Pr)4 (red) after addition of one equivalent of 1 (green) and upon addition of one equivalent of 25 (blue).
  • Fig. S33. Excerpt of the NMR spectrum showing the methyl doublet of Ti(Oi-Pr)4 (red) after addition of one equivalent of 1 (green) and upon addition of one equivalent of 25 (blue).
  • Fig. S34. CD intensity at 375 nm (triangle) and 470 nm (diamond) for the complex obtained from Ti(Oi-Pr)4, 1, and (1R,2R)-25 (blue) and for (1S,2S)-25 (red).
  • Fig. S35. X-ray structure of bis(2-methoxy-1-naphthyl)ketone, 3.
  • Fig. S36. X-ray structure of bis(2-hydroxy-1-naphthyl)ketone, 1.
  • Table S1. Ee determination of N-methylephedrine.
  • Table S2. Experimentally determined concentrations of five samples of varying concentrations of 14 using the fluorescence response at 600 nm.
  • Table S3. Ee determination of hydrobenzoin.
  • Table S4. Experimentally determined concentrations of five samples of varying concentrations of 25 using the fluorescence response at 600 nm.
  • Table S5. Comparison of calculated and actual ee and concentration values of hydrobenzoin obtained by asymmetric Sharpless dihydroxylation.

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