Science Advances

Supplementary Materials

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  • Supplementary Text
  • scheme S1. Pathway to synthesize chiral Boc-HL.
  • scheme S2. Pathway to synthesize chiral HL.
  • scheme S3. Proposed reaction mechanism for visible light–driven asymmetric α-alkylation of aldehydes in the presence of chiral MOFs.
  • fig. S1. 1H NMR spectrum of 2-aminoterephthalic acid.
  • fig. S2. 1H NMR spectrum of N-(tert-butoxycarbonyl)-prolinal.
  • fig. S3. 1H NMR spectrum of Boc-HL without hydrogenation.
  • fig. S4. 1H NMR spectrum of Boc-HL.
  • fig. S5. 13C NMR spectrum of Boc-HL.
  • fig. S6. 1H NMR spectrum of HL.
  • fig. S7. Absorption spectra (200 to 500 nm) of chiral N-Boc-prolinal, H2BDC-NH2, and chiral HL.
  • fig. S8. FT-IR spectra of chiral Boc-HL, Boc-Zn-MOF, Boc-Zr-MOF, and Boc-Ti-MOF.
  • fig. S9. TGA of Boc-metal-MOFs.
  • fig. S10. SEM images of Zn-MOF, Zr-MOF, and Ti-MOF.
  • fig. S11. N2 adsorption-desorption isotherms of Boc-Zn-MOF and Zn-MOF.
  • fig. S12. N2 adsorption-desorption isotherms of Boc-Zr-MOF and Zr-MOF.
  • fig. S13. N2 adsorption-desorption isotherms of Boc-Ti-MOF and Ti-MOF.
  • fig. S14. FT-IR spectra of Boc-Ti-MOF and Ti-MOF.
  • fig. S15. Photos of catalysts, Zn-MOF, Zr-MOF, and Ti-MOF.
  • fig. S16. Photos illustrating the experimental process of photocatalysis.
  • fig. S17. GC-MS result for standard reaction in absence of light illumination.
  • fig. S18. GC-MS result for catalytic reaction with pure chiral HL at 20°C and under 25-W illumination.
  • fig. S19. GC-MS result for catalytic reaction with chiral Zn-MOF at 20°C and under 25-W illumination.
  • fig. S20. GC-MS result for catalytic reaction with chiral Zr-MOF at 20°C and under 25-W illumination.
  • fig. S21. GC-MS result for catalytic reaction with chiral Ti-MOF at 20°C and under 25-W illumination.
  • fig. S22. MS spectrum of 3-phenylpropionaldehyde.
  • fig. S23. MS spectrum of cis-6-nonenal.
  • fig. S24. MS spectrum of diethyl bromomalonate.
  • fig. S25. MS spectrum of product 1.
  • fig. S26. MS spectrum of product 2.
  • fig. S27. Reaction time–dependent conversion using Ti-MOFs as catalyst at 20°C.
  • fig. S28. Representative 1H NMR spectrum for determining ee value of the product obtained with racemic Ti-MOF (3-phenylpropionaldehyde as substrate).
  • fig. S29. Representative 1H NMR spectrum for determining ee value of the product obtained with S-Ti-MOF (3-phenylpropionaldehyde as substrate).
  • fig. S30. Representative 1H NMR spectrum for determining ee value of the product obtained with R-Ti-MOF (3-phenylpropionaldehyde as substrate).
  • fig. S31. XRD patterns of chiral Ti-MOF after recycle use for three times.
  • fig. S32. FT-IR spectra of 3-phenylpropionaldehyde, Ti-MOF, and their mixture.
  • fig. S33. X-ray photoelectron spectroscopy spectra of Ti-MOF and mixture of
    Ti-MOF and diethyl bromomalonate.
  • fig. S34. FT-IR spectra of bromomalonate, Ti-MOF, and their mixture.
  • fig. S35. Diagram of energy level for alkyl bromide and Ti-MOF (versus saturated calomel electrode).
  • table S1. Catalytic performance with error ranges.
  • table S2. Contrast tests by using Boc-protected chiral ligand, corresponding MOFs, or large output of light source.
  • table S3. Catalytic property of reused MOFs.
  • References (60–66)

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