Zinc Complexes Formed by 2 , 2 ’-Bipyridine and 1 , 10-Phenanthroline Moieties Combined with 2-Azanorbornane : Modular Chiral Catalysts for Aldol Reaction

Chiral scaffolds of 2-azabicyclo[2.2.1]heptane and 2-azabicyclo[3.2.1]octane were used for the construction of new modular catalysts containing complexing moieties pyridine, 2,2′-bipyridine and 1,10-phenanthroline appended by an imine linkage. The coordination abilities of the new ligands towards Zn(II) were investigated using NMR and UV spectroscopy. The plausible structures of the [ZnL2]2+ and [ZnLXn](2−n)+ complexes formed were established by comparison of the experimental and DFT-calculated NMR spectra. The catalytic application of the [ZnLXn](2−n)+-type complexes in the asymmetric aldol reaction of ketones with aromatic aldehydes produced an excess of the respective syn-aldols in up to >98% ee.

Table S1 1 H NMR chemical shifts of ligand 11 and its zinc complexes Table S2. 13C NMR chemical shifts of ligand 11 and its zinc complexes Table S3. 1 H NMR chemical shifts of ligand 10 and its zinc complexes Table S4. 13C NMR chemical shifts of ligand 10 and its zinc complexes Table S5. 1 H and 13 C NMR chemical shifts of ligand 9 and its zinc complex  Table S1 1 H NMR chemical shifts of ligand 11 and its zinc complexes (methanol-d4, 300 K; L = ligand 11, X = OAc  ).Numbering scheme for ligand 11 is shown.Entries 4 and 5 show the chemical shift changes with the most pronounced differences ( 0.2 ppm) listed in bold.Table S3 1 H NMR chemical shifts of ligand 10 and its zinc complexes (methanol-d4, 300 K; L = ligand 10, X = OAc  ).Numbering scheme for ligand 10 is shown.Entries 4 and 5 show the chemical shift changes with the most pronounced differences listed in bold.Table S4. 13C NMR chemical shifts of ligand 10 and its zinc complexes (methanol-d4.300 K; L = ligand 10, X = OAc  ).Quaternary carbons not included.Numbering scheme for ligand 10 is shown.3" N Table S5. 1 H and 13 C NMR chemical shifts of ligand 9 and its zinc complex (methanol-d4.300 K; L = ligand 9, X = OAc  ).Quaternary carbons not included.Numbering scheme for ligand 9 is shown.

Figure S9 .
Figure S1. 1 H NMR and 13 C NMR spectra of 4 Figure S2. 1 H NMR and 13 C NMR spectra of 6 Figure S3. 1 H NMR and 13 C NMR spectra of 9 Figure S4. 1 H NMR and 13 C NMR spectra of 10 Figure S5. 1 H NMR and 13 C NMR spectra of 11 Figure S6. 1 H NMR and 13 C NMR spectra of 12 Figure S7. 1 H NMR and 13 C NMR spectra of 13 Figure S8. 1 H NMR and 13 C NMR spectra of 14 Figure S9.Comparison of 1 H NMR spectra of monomeric Zn(II) and Cd(II) complexes of ligand 11

Figure S10 .
Figure S10.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of ligand 10 (compact conformation) and the correlation of shift values for particular positions.

Figure S11 .
Figure S11.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of ligand 10 (open conformation) and the correlation of shift values for particular positions.

Figure S12 .
Figure S12.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of ligand 11 (compact conformation) and the correlation of shift values for particular positions.

Figure S15 .
Figure S15.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of 4N-coordinated [ZnL] 2+ complex of ligand 10 and the correlation of shift values for particular positions.

Figure S16 .
Figure S16.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of 4N-coordinated [ZnL2] 2+ complex of ligand 10 and the correlation of shift values for particular positions.

Figure S18 .Figure S19 .Figure S20 .
Figure S18.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of 2N-coordinated [ZnL] 2+ complex of ligand 11 and the correlation of shift values for particular positions.

Figure S21 .
Figure S21.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of [ZnL(OAc)2] complex of ligand 11 and the correlation of shift values for particular positions.

Table S6 .
DFT calculated energiesElectronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016

Ligand 10 -a compact conformation Table S7. Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm) *
*Average values of calculated chemical shifts for ortho-H, meta-H and 1'-Me were given.

Table S8 . Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)*
*Average values of calculated chemical shifts for ortho-H, meta-H and 1'-Me were given.

Table S9 . Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)*
*Average values of calculated chemical shifts for ortho-H, meta-H and 1'-Me were given.

Table S10 . Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)*
Figure S13.Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of ligand 11 (open conformation) and the correlation of shift values for particular positions.experimental experimental 1 H NMR shift Compound 10, [

ZnL] 2+ complex. (N2) coordination Table S11. Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)*
Comparison of experimental and DFT calculated averaged chemical 1 H NMR shift patterns of 2N-coordinated [ZnL] 2+ complex of ligand 10 and the correlation of shift values for particular positions.

Table S13 . Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)*
*Average values of calculated chemical shifts for the two subunits were given.

Table S14 . Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)*
Average values of calculated chemical shifts for the two subunits were given. *

Table S15 . Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)
calculatedCompound

Table S16 . Comparison of DFT calculated and experimental 1 H NMR chemical shifts (methanol-d4, all values in ppm)*
*Average values of calculated chemical shifts for the two subunits were given.