Homochiral 2D Porous Covalent Organic Frameworks for Heterogeneous Asymmetric Catalysis

Transcription

1 Homochiral 2D Porous Covalent Organic Frameworks for Heterogeneous Asymmetric Catalysis Xiuren Wang, Xing Han, Jie Zhang, Xiaowei Wu, Yan Liu*, and Yong Cui*,, School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai , China. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin , China. Table of Content 1. Materials and general procedures 2. Synthesis of CCOFs 3. General procedure for asymmetric catalysis 4. Tables S1 Comparison with different heterogeneous catalysts in the reaction 5. Figure S1 FT-IR spectra 6. Figure S2 NMR spectra of the CCOFs and monomers 7. Figure S3 ESI-MS spectra 8. Figure S4 The Solid-CD spectra 9. Figure S5 TGA curves 10. Figure S6 SEM and TEM 11. Figures S7&S8 PXRD patterns 12. Figure S9 BET plots 13. Figures S10-S13 Structural modeling and PXRD analysis of COFs 14. Tables S2&S3 Fractional atomic coordinates for the unit cell of COFs 15. Figure S14 Spectra data of the catalysis 16. Figure S15 Calculated space filling model of different Aromatic Aldehydes S1

2 1. Materials and general procedures General. All the chemicals are commercial available, and used without further purification. All solvents were dried and distilled according to conventional methods. The IR (KBr pellet) spectra were recorded ( cm -1 region) on a Nicolet Magna 750 FT-IR spectrometer. The CD spectra were recorded on a J-800 spectropolarimeter (Jasco, Japan). Powder X-ray diffraction data (PXRD) were collected on a DMAX2500 diffractometer using Cu Kα radiation. Thermogravimetric analyses (TGA) were carried out in an air atmosphere with a heating rate of 20 o C/min on a STA449C integration thermal analyzer. SEM was conducted on a JEOL JSM-7401F electron microscope. 1 H and 13 CNMR experiments were carried out on a MERCURY plus 400 spectrometer operating at resonance frequencies of 400 MHz. Analytical high performance liquid chromatography (HPLC) was performed on YL-9100 HPLC with UV detection at 220 nm. Analytical CHIRALCEL OD-H and AD-H columns (4.6 mm 25 cm) from Daicel were used. Absolute stereochemistry was assigned by comparison of optical rotation with reported values. The porous properties of the covalent organic frameworks (COFs) were investigated by nitrogen adsorption and desorption at 77.3 K using ASAP 2020 V4.00 (V4.00 H) Serial #: 1674 from USA. Pore size distributions and pore volumes were derived from the adsorption isotherms. Samples were pretreated by the supercritical carbon dioxide and degassed at 100 C for 4 h under high vacuum before analysis. The theoretical surface area was calculated by Atom Volumes &Surface(Materials Studio, version 7.0). S2

3 2. Synthesis of the CCOFs (R,R)-C was synthesized according to the published procedure (Wang, X.; Zhang, J.; Liu, Y and Cui, Y. Bull. Chem. Soc. Jpn. 2014, 87, 435). 2.1 Synthesis of (R,R)-TTA: Magnesium (1.08 g, 45 mmol), anhydrous THF (30 ml), and a grain of iodine were added to a flame-dried three-necked flask. B (9.16 g, 40 mmol) in THF (80 ml) was then added dropwise to the solution at a rate sufficient to maintain a vigorous reflux. After that, the mixture was stirred and heated at 50 o C for another 2 h. A (1.46 g, 6.7 mmol) in THF (50 ml) was added dropwise to the solution at 0 o C over 1 h, and then the reaction mixture was kept for an additional 12 h at room temperature. The saturated 10% HCl solution was added carefully to quench the reaction until the ph value is reached to 2 at 0 o C. and then the reaction mixture was stirred for an additional 24 h at room temperature. The organic layer was separated, and the aqueous phase was extracted with diethyl ether (3 50 ml). The combined organic phase was then dried over Na 2 SO 4 and concentrated. The crude material was purified by flash chromatography on silica gel (hexane: ethyl acetate = 60 : 40) to give product (1.98 g, 51% yield) as a yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 9.91 (s, 2H), 9.85 (s, 2H), 7.83 (d, J = 8.5 Hz, 4H), (m, 8H), S3

4 7.50 (d, J = 8.4 Hz, 4H), 5.53 (s, 2H), 4.49 (s, 2H), 1.13 (s, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 192.2, 191.9, 151.0, 148.6, 135.3, 135.3, 129.5, 129.0, 128.8, 128.2, 109.8, 80.8, 77.7, FTIR (KBr pellet, ν/cm -1 ): 3329 (s), 2986 (w), 2922 (w), 1912 (w), 1702 (s), 1606 (s), 1575 (m), 1418 (w), 1383 (m), 1308 (m), 1240 (w), 1214 (s), 1174 (m), 1064 (m), 1014(w), 886 (w), 845 (m), 817 (s), 762 (m), 668 (w), 517 (w). ESI-MS m/z: (Calcd m/z for [M-H] - ). 2.2 Synthesis of (R,R)-TTPA:(R,R)-C(1.56 g, 2.0 mmol), (4-formylphenyl)boronic acid (1.50 g, 10.0 mmol), K 3 PO 4 (6.4 g, 24 mmol) and Pd(P(Ph) 3 ) 4 (230 mg, 0.2 mmol ) in dioxane/h 2 O (3/1 v/v, 24 ml) were degassed for 10 min. the suspension was stirred under N 2 at 100 o C for 24 h. After cooling to room temperature, the mixture was concentrated and extracted with EtOAc/H 2 O. The organic phase was dried over anhydrous Na 2 SO 4 and then concentrated under reduced pressure to remove the solvent. The crude product was purified by silica gel column chromatography (hexanes/ethyl acetate (4:3 v/v) to afford (R,R)-c. Yield: (742.6 mg, 42%). 1 H NMR (400 MHz, CDCl 3 ) δ (d, J = 4.4 Hz, 2H), (d, J = 4.0 Hz, 2H), 7.96 (dd, J = 8.2, 2.0 Hz, 4H), 7.89 (dd, J = 8.2, 2.4 Hz, 4H), 7.80 (d, J = 7.6 Hz, 4H), 7.74 (d, J = 8.4 Hz, 4H), 7.67 (m, 8H), 7.52 (q, J = 8.8 Hz, 8H), 4.71 (d, J = 2.4 Hz, 2H), 4.55 (s, 2H), 1.22 (s, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 192.0, 191.9, 146.5, 146.4, 145.7, 142.9, 138.7, 138.3, 135.0, 130.3, 130.2, 129.2, 128.3, 127.4, 127.4, 127.0, 126.2, 109.5, 81.1, 77.7, FTIR (KBr pellet, ν/cm -1 ): 3348 (m), 3025 (w), 2985 (w), 2885 (w), 1911 (w), 1702 (s), 1605 (s), 1577 (w), 1495 (w), 1384 (w), 1310 (w), 1214 (s), 1171 (m), 1061(m), 1006 (w), 842 (m), 816 (s), 776 (m), 664 (w), 523 (w). ESI-MS m/z: (Calcd m/z for [M-H] - ). 2.3 Synthesis of CCOF-1: 25 ml schlenk was charged with (R,R)-TTA (145 mg, 0.25 mmol) and 4,4 -diaminodiphenylmethane (4,4 -DADPM) (99 mg, 0.5 mmol), anhydrous 1, 4-dioxane (6 ml). The resulting mixture was sonicated for a few minutes until the solid was completely dissolved. The solution was then added 9 M acetic acid (1.5 ml), and the Schlenk was flash frozen at 77 K using the liquid nitrogen bath, evacuated and sealed by Teflon valve. Upon warming to room temperature, the Schlenk was placed in an oven and heated at 100 C for 3 days. After heating at 120 ºC for 72 h, gray solid at the bottom of the tube was isolated by hot filtration and washed with anhydrous 1, 4-dioxane. The powder collected was then solvent exchanged with THF for three times and acetone for one time and then dried S4

5 at 100 o C under vacuum for 24 h to give a gray powder (158 mg, 70 % yield). FTIR (KBr pellet, ν/cm -1 ): 3329 (s), 3027 (w), 2981 (w), 2296 (w), 1909 (w), 1699 (w), 1624 (s), 1602 (m), 1565 (w), 1506 (s), 1410 (w), 1377 (w), 1309 (w), 1199 (m), 1171 (m), 1057 (s), 1016(m), 974 (w), 887 (m), 832 (s), 764 (m), 714 (w), 589 (w). 2.4 Synthesis of CCOF-2: This COF was synthesized following the similar method as described about CCOF-1 by using (R,R)-TTPA (132 mg, 0.15 mmol) and 4,4 -diaminodiphenylmethane (4,4 -DADPM) (59.5mg, 0.3 mmol). The powder collected was then solvent exchanged with THF for three times and acetone for one time and then dried at 100 o C under vacuum for 24 h to give a gray powder (116 mg, 64% yield). FTIR (KBr pellet, ν/cm -1 ): 3346 (m), 3026 (w), 2980 (w), 2886 (w), 1913 (w), 1700 (w), 1623 (m), 1600 (m), 1501 (s), 1373 (w), 1309 (w), 1245 (w), 1199 (w), 1172 (m), 1057 (w), 1006 (m), 915 (w), 887 (m), 823 (s), 777 (w), 731 (w), 549 (w). 2.5 Activation of the CCOF Standard activation: The powder collected was then solvent exchanged with THF for three times and anhydrous acetone for one time and then dried at 100 o C under vacuum for 24 h. Activation for BET measurement: The COF powder was immersed in anhydrous THF, and the solvent was exchanged with fresh THF for three times and anhydrous acetone for one time. The wet sample was then transfer to a super critical drier, in which the sample was washed with five times of liquid CO 2, and exchanged with fresh CO 2 for 5 times with the interval of half hour. The system was heat up to 45 ºC to bring about the supercritical state of the CO 2, which was bleed after half hour in very slow flow rate to ambient pressure. The sample was then transferred to vacuum chamber and evacuated to 20 mtorr 100 C for 4 h, yielding white powder. 3. General procedure for asymmetric catalysis 3.1 The diethylzinc addition reactions catalyzed by CCOF/Ti: The catalytic process was similar, here, take the procedure of CCOF-1/Ti catalyzed reactions as an example. To a dry sample of CCOF-1 (18.1 mg, 0.02 mmol) in 1 ml of anhydrous toluene was added Ti(O i Pr) 4 (85 mg, 0.3 mmol), and the resulting mixture was stirred for 1 h. The solvent and excess Ti(O i Pr) 4 were evaporated off under high vacuum. The S5

6 residue was degassed and benzaldehyde (10.6 mg, 0.1 mmol) in toluene (1.0 ml) was added. The reaction mixture was cooled to -30 o C under N 2 atmosphere, diethylzinc in hexane (200 μl, 1.0 M, 0.2 mmol) were then added to the vigorous stirring suspension and allowed to react for 10 h at -30 o C. The effect of the stirring is order to react uniformly. The reaction mixture was quenched by the addition of 1 ml of saturated ammonium chloride and 1 ml of diethyl ether. The organic layer was analyzed by 1 H NMR and HPLC to give conversion and ee values. Notably, the use of excess amount (3 quiv.) of Ti(OiPr) 4 to modify the CCOFs is to make sure Taddol units in the framework react completely with Ti(IV) ions for achieving high activity. Decreasing the amount of Ti(OiPr) 4 to, for example, 2.5 equivalent led to the conversion of benzylaldehyde decreasing from 99 to 90% under otherwise identical conditions. 3.2 The diethylzinc addition reactions catalyzed by TADDOL/Ti: The procedure was the same as the above catalytic experiments. Notably, the asymmetric addition of dialkyl zinc to aldehydes have been well studied in homogeneous catalysis, See: (a) Cozzi, P. G.; Kotrusz, P. J. Am. Chem. Soc. 2006, 128, (b) García, C.; LaRochelle, L. K.; Walsh, P. J. J. Am. Chem. Soc. 2002, 124, (c) Wieland, L. C.; Deng, H.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127, (d) Balsells, J.; Davis, T. J.; Carroll, P.; Walsh, P. J. J. Am. Chem. Soc. 2002, 124, (e) Qiu, J.; Guo, C.; Zhang, X. J. Org. Chem. 1997, 62, Recycling Experiments: The catalytic process was the same as the above catalytic experiments. After the reaction, the solution was removed by centrifugation quikly, the polymer was rinsed quickly with anhydrous toluene and isolated by centrifugation, then Ti(O i Pr) 4 (80 mg, 0.28 mmol) were added and stirred for 1.0 h under N 2. Benzaldehyde (10.6 mg, 0.1 mmol) in toluene (1.0 ml) were added, followed by diethylzinc in hexane (200 μl, 1.0 M, 0.2 mmol) at -30 o C under N 2. Then the reaction mixture was stirred at -30 o C for a new run. S6

7 4. Table S1. Comparison with different heterogeneous catalysts in the addition of Et 2 Zn to aromatic aldehydes. (a) Wu, C.; Hu, A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2005, 127, (b) Ma, L.; Falkowski, J. M.; Abney, C.; Lin, W. Nat. Chem. 2010, 2, 838. (c) Wang, X.; Zhang, J.; Liu, Y.; Cui, Y. Bull. Chem. Soc. Jpn. 2014, 87, 435. (d) An, W.; Han, M.; Wang, C.; Yu, S.; Zhang Y.; Bai, S.; Wang, W. Chem. Eur. J. 2014, 20, S7

8 5. Figure S1. FT-IR spectra for a) CCOF-1 and b) CCOF-2. a) Transmittance 4, 4'-DADPM (R,R)-TTA 1702(C=O) CCOF (C=N) Wavenumber (cm -1 ) b) Transmittance 4, 4'-DADPM (R,R)-TTPA 1702(C=O) CCOF (C=N) Wavenumber (cm -1 ) S8

9 6. Figure S2. NMR spectra of the CCOFs and related monomers S9

10 S10

11 S11

12 7. Figure S3. ESI-MS spectra of the TADDOL-derived tetraaldehydes 8. Figure S4. The solid-state CD spectra of the CCOFs. (R,R)-CCOF-1 (S,S)-CCOF-1 S12

13 (R,R)-CCOF-2 (S,S)-CCOF-2 9. Figure S5. TGA curves of the CCOFs S13

14 10. Figure S6. SEM images of (a) CCOF-1 and (c) CCOF-2; and TEM images of (b) CCOF-1 and (d) CCOF-2. CCOF-1 CCOF-2 CCOF-1 CCOF-2 S14

15 11. Figures S7&S8. PXRD patterns Figure S7. PXRD of the CCOFs after treating by different conditions (a) and (c): The powders were soaked in different solvents in 10 days and dried in air. (b) and (d): The above solvent-treated powders was solvent exchanged with THF three times and then dried at 100 o C under vacuum for 24 h. (e) and (f): The COFs after measuring N 2 adsorption-desorption isotherms (a) Pristine CCOF-1 Unactivated CCOF-1 after soaking in Toulene for 10 days Unactivated CCOF-1 after soaking in MeOH for 10 days Unactivated CCOF-1 after soaking in THF for 10 days Unactivated CCOF-1 after soaking in H 2 O for 10 days theta degree (b) Activated CCOF-1 after soaking in Toulene for 10 days Activated CCOF-1 after soaking in MeOH for 10 days Activated CCOF-1 after soaking in THF for 10 days Activated CCOF-1 after soaking in H 2 O for 10 days theta (degree) S15

16 (c) Pristine CCOF-2 Unactivated CCOF-2 after soaking in Toulene for 10 days Unactivated CCOF-2 after soaking in MeOH for 10 days Unactivated CCOF-2 after soaking inthf for 10 days Unactivated CCOF-2 after soaking in H 2 O for 10 days (d) theta (degree) Activated CCOF-2 after soaking in Toulene for 10 days Activated CCOF-2 after soaking in MeOH for 10 days Activated CCOF-2 after soaking in THF for 10 days Activated CCOF-2 after soaking in H 2 O for 10 days theta (degree) S16

17 (e) Pritstine CCOF-1 CCOF-1 after measuring N 2 adsorption-desorption isotherms theta (degree) (f) Pritstine CCOF-2 CCOF-2 after measuring N 2 adsorption-desorption isotherms theta (degree) S17

18 11.2. Figure S8. PXRD of the recycling catalysts (a) Experimental PXRD of of CCOF-1 JTU-1 PXRD of JTU-1/Ti CCOF-1/Ti PXRD of JTU-1/Ti CCOF-1/Ti after 53 cycles theta (degree) (b) Experimental PXRD of CCOF-2 PXRD of CCOF-2/Ti PXRD of CCOF-2/Ti after 5 cycles Theta (degree) S18

19 12. Figure S9. BET plots of the CCOFs BET Surface Area:266.0 m 2 /g 1/[Q(Po/P - 1 )] CCOF-1 y= x R 2 = P/Po /[Q(Po/P - 1 )] BET Surface Area:334.9 m 2 /g CCOF-2 y= x R 2 = P/Po S19

20 13. Figures S10-S13. Structural modeling and PXRD Analysis of the CCOFs Structure Simulation: Molecular modeling of these COFs was generated with the Materials Studio (ver. 7.0) suite of programs. Pawley refinement was carried out using Reflex, a software package for crystal determination from PXRD pattern. Unit cell dimension was set to the theoretical parameters. The Pawley refinement was performed to optimize the lattice parameters iteratively until the R wp value converges and the overlay of the observed with refined profiles shows good agreement. The lattice models (e.g., cell parameters, atomic positions, and total energies) were then fully optimized using MS Forcite molecular dynamics module (universal force fields, Ewald summations) method. For CCOF-1, considering the geometry of the precursors and the connection patterns, only a few topologies are reasonable Figure S10 Space-filling models of CCOF-1 with different nets: a) sp, b) dp, c) bsp, d) tp. Carbon, gray; Nitrogen, blue; Oxygen, red; Hydrogen atoms are omitted. S20

21 13.2. Figure S11 The calculated PXRD profiles: sp (red), dp (bule), tp (pink), bsp (green) The experimental pattern was also presented (black). For CCOF-1 dp, tp, bsp topology, their calculated total energy(959.8, and kcal / mol respectively) is higher than sp topology (636.6 kcal / mol), and the calculated PXRD pattern (Figure S11) has shown several peaks below 6 degrees that disagree with the experimental data. For sp topology (P2 1 space group, also see Figure S11 in SI), the calculated PXRD pattern was in agreement with experimental data. In addition, Pawley refinement yielded an XRD pattern that is in good agreement with the experimental data and the R wp and R p values was 6.97% and 5.82%. For CCOF-2, considering the geometry of the precursors and the connection patterns, only a few topologies are reasonable. For sp, bdp and fp topology, their calculated total energy (914.4, and kcal / mol) is higher than tp topology (878.8 kcal / mol), the calculated PXRD pattern (Figure S12) has shown several peaks below 7 degrees that disagree with the experimental data. For tp topology (P2 1 space group, also see Figure S12 in SI), the calculated PXRD pattern was in agreement with experimental data. In addition, Pawley refinement yielded an XRD pattern that is in good agreement with the experimental data and the R wp and R p values was 4.25% and 3.03%. S21

22 13.3. Figure S12. Space-filling models of CCOF-2 with different nets: a) sp, b) tp, c) bdp, d) fp. Carbon, gray; Nitrogen, blue; Oxygen, red; Hydrogen atoms are omitted Figure S13. The calculated PXRD profiles: tp (red), sp (bule), fp (pink), bdp (green). The experimental pattern was also presented (black). 14. Table S2 and S3. Fractional atomic coordinates and unit cell parameters Table S2. Fractional atomic coordinates of for the unit cell of sp net CCOF-1 with P2 1 space group. S22

23 CCOF-1: Space group: P2 1 a = Å, b = Å, c = Å α = 90.0, β = , γ = 90.0 Atom x y z C C C C C C C C C C C C C N C C C C C C C C N C C C C C C C C C C N C C C C S23

24 C C C N C O O O O 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 S24

25 N C C C C C C C C N C C C C C C C C C C N C C C C C C C N C O O O O C C C C C C C C C S25

26 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 H H H H H H H H H H H H H H S26

27 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 S27

28 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 Table S3. Fractional atomic coordinates for the unit cell of tp net CCOF-2 with P2 1 space group. CCOF-2: Space group: P2 1 a = Å, b = Å, c = Å α = 90.0, β = , γ = 90.0 Atom x y z C C C C C C C S28

29 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 N C C C C C C C N C C S29

30 C C C C C C C N C C C C C C N C O O O O C C C C C C C C C C C C C C C C C C C C C S30

31 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 C C C N C S31

32 C C C C C C N C C C C C C C C C N C C C C C C N C O O O O C C C C C C C C C C C C S32

33 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 H H H H H H H H H H H S33

34 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 S34

35 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 S35

36 H H H H H H H H H H H H H H H H H H H H H H H H Figure S14. Spectra data of the catalysis 15.1 NMR and HPLC of the secondary alcohols obtained with CCOF-1/Ti (S)-1-phenylpropan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 90%. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), 4.59 (td, J = 6.7, 3.1 Hz, 1H), 1.92 (s, 1H), (m, 2H), 0.91 (t, J = 7.4 Hz, 3H). S36

37 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S37

38 (R)-1-phenylpropan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 90%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total (S)-1-(p-tolyl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel AD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 93%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.23 (d, J = 8.1 Hz, 2H), 7.16 (d, J = 7.8 Hz, 2H), 4.56 (t, J = 6.6 Hz, 1H), 2.35 (s, 3H), (m, 3H), 0.91 (t, J = 7.4 Hz, 3H). Serial Number Retention Time [min] Area [mabs*s] Type Area % BB S38

39 BB The Total Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total (S)-1-(4-chlorophenyl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 90%. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), 4.59 (t, J = 6.5 Hz, 1H), 1.91 (s, 1H), 1.81 S39

40 1.72 (m, 2H), 0.90 (t, J = 7.4 Hz, 3H). Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S40

41 (S)-1-(naphthalen-2-yl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 90/10; flow rate = 0.5 ml/min; t major = min, t minor = min; ee = 94%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.83 (dd, J = 7.0, 2.7 Hz, 3H), 7.77 (s, 1H), (m, 3H), 4.77 (t, J = 6.6 Hz, 1H), 2.02 (s, 1H), (m, 2H), 0.94 (t, J = 7.4 Hz, 3H). Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S41

42 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S-(E)-1-phenylpent-1-en-3-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 95/5; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 91%. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 5H), 6.57 (d, J = 15.9 Hz, 1H), 6.21 (dd, J = 15.9, 6.8 Hz, 1H), 4.20 (q, J = 6.5 Hz, 1H), 1.98 (s, 1H), (m, 2H), 0.96 (t, J = 7.4 Hz, 3H). S42

43 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S43

44 (S)-1-(pyren-4-yl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 90/10; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 82.0%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.32 (d, J = 9.3 Hz, 1H), (m, 4H), 8.08 (d, J = 9.4 Hz, 1H), (m, 3H), 5.69 (t, J = 6.4 Hz, 1H), 2.17 (s, 1H), (m, 2H), 1.04 (t, J = 7.4 Hz, 3H). Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BV The Total S44

45 HO 1-(coronen-1-yl)propan-1-ol: 1 H NMR (400 MHz, DMSO) δ 9.25 (d, J = 9.2 Hz, 1H), 9.15 (s, 1H), (m, 9H), (m, 1H), 5.78 (d, J = 4.0 Hz, 1H), (m, 1H), (m, 1H), 1.18 (t, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, DMSO) δ , , , , , , , , , , , , , , , 72.47, 32.75, S45

46 13.2 NMR and HPLC of the secondary alcohols obtained with CCOF-2/Ti. (S)-1-phenylpropan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 85%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB VB The Total (R)-1-phenylpropan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 85%. S46

47 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total (S)-1-(p-tolyl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel AD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 88%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total (S)-1-(4-chlorophenyl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate= 1.0 ml/min; t major = min, t minor = min; ee = 86%. S47

48 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total (S)-1-(naphthalen-2-yl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 90/10; flow rate = 0.5 ml/min; t major = min, t minor = min; ee = 95%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S-(E)-1-phenylpent-1-en-3-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 95/5; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 85%. S48

49 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total (S)-1-(pyren-4-yl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 90/10; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 74%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total HPLC of the secondary alcohols obtained with homogeneous TADDOL/Ti The ee values of the alcohol products derived from C 6 H 5 CH=CHO, C 6 H 5 CHO are used the reported date in Bull. Chem. Soc. Jpn. 2014, 87, 435 (Wang, X. et al.) S49

50 (S)-1-phenylpropan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 90%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB VB The Total Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S50

51 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total (S)-1-(naphthalen-2-yl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 90/10; flow rate = 0.5 ml/min; t major = min, t minor = min; ee = 93%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S51

52 (S)-1-(pyren-4-yl)propan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 90/10; flow rate = 1.0 ml/min; t major = min, t minor = min; ee = 78%. Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total Catalytic recycling results by CCOF-1/Ti : (S)-1-phenylpropan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min. The 1 st run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S52

53 The 2 nd run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB VB The Total The 3 rd run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total The 4 th run S53

54 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total The 5 th run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total Catalytic recycling results by CCOF-2/Ti (S)-1-phenylpropan-1-ol: Optical purity is determined by HPLC with a ChiralCel OD-H column: 25 o C; hexane/iproh = 98/2; flow rate = 1.0 ml/min. The 1 st run S54

55 Serial Number Retention Time [min] Area [mabs*s] Type Area % BB VB The Total The 2 nd run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total The 3 rd run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S55

56 The 4 th run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total The 5 th run Serial Number Retention Time [min] Area [mabs*s] Type Area % BB BB The Total S56

57 16 Figure S15. Calculated space filling model of different aromatic aldehydes. The space-filling models were calculated by Materials Studio (7.0), and were fully optimized using MS Forcite molecular dynamics module (universal force fields, Ewald summations) method. S57