Magnesium-mediated Nucleophilic Borylation of Carbonyl Electrophiles

Transcription

1 Supplementary Information for Magnesium-mediated Nucleophilic Borylation of Carbonyl Electrophiles Anne-Frédérique Pécharman, Michael S. Hill,* Claire L. McMullin* and Mary F. Mahon Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK -S1-

2 Figure S1: 1 H NMR (500 MHz, toluene-d 8 ) spectrum of a reaction of 5 and 0.9 equivalents of benzophenone, illustrating the selectivity of the formation of compound 10 (Blue stars). Green stars 5; red stars 11. * * * * * * * * * * * * * * -S2-

3 Figure S2: 11 B{ 1 H} NMR (160 MHz, toluene-d 8 ) spectrum of an in situ reaction of 5 and 0.9 equivalents of benzophenone. Green star 5; red star 11. * * * -S3-

4 Figure S3: 1 H NMR (500 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 10. -S4-

5 Figure S4: 13 C{ 1 H} NMR (126 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 10. -S5-

6 Figure S5: 11 B{ 1 H} NMR (160 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 10. -S6-

7 Figure S6: Stacked 1 H NMR (500 MHz, toluene-d 8 ) spectra of the reaction of compound 10 and 4- dimethylaminopyridine (DMAP) to form compound 7; green spectrum, compound 10; red spectrum, after adding 1 equivalent of DMAP; blue spectrum, crystallized sample of compound 7. -S7-

8 Figure S7: 1 H NMR (500 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 11. -S8-

9 Figure S8: 13 C{ 1 H} NMR (126 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 11. -S9-

10 Figure S9: 11 B{ 1 H} NMR (160 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 11. -S10-

11 Figure S10: In situ 1 H NMR (500 MHz, toluene-d 8 ) spectrum of a reaction of compound 5 and 1 equivalent of 9-fluorenone showing the formation of compound 12 and only 50% consumption of compound 10. -S11-

12 Figure S11: Resultant 11 B{ 1 H} NMR (160 MHz, toluene-d 8 ) spectrum of a reaction of compound 5 and 1 equivalent of 9-fluorenone. -S12-

13 Figure S12: 1 H NMR (500 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 12. -S13-

14 Figure S13: 13 C{ 1 H} NMR (126 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 12. -S14-

15 Figure S14: 11 B{ 1 H} NMR (160 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 12. -S15-

16 Figure S15: 1 H NMR (500 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 13. -S16-

17 Figure S16: 13 C{ 1 H} NMR (126 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 13. -S17-

18 Figure S17: 11 B{ 1 H} NMR (160 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 13. -S18-

19 Figure S18: 1 H NMR (500 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 14. -S19-

20 Figure S19: 13 C{ 1 H} NMR (126 MHz, toluene-d 8 ) spectrum of a crystallized sample of compound 14. -S20-

21 Figure S20: 11 B{ 1 H} NMR (160 MHz, v) spectrum of a crystallized sample of compound 14. -S21-

22 Single Crystal X-ray Diffraction analysis. Single Crystal X-ray diffraction data for compounds were collected using CuKα (λ = Å) on a SuperNova, Dual Cu at zero, EosS2 diffractometer. The crystals were kept at 150(2) K during data collections. Using Olex2, 1 the structures were solved via SHELXS 2 and refined with the ShelXL refinement package using Least Squares minimisation. The asymmetric unit of compound 10 contains ½ of a molecule of hexane in addition to one molecule of the magnesium-containing complex. H48, attached to C48, was located and refined without restraints. In 13, the asymmetric unit contains one dimer molecule and two solvent regions. The first of the latter (based on C82) comprises one full molecule of toluene which is disordered in its entirety over 2 positions in a 60:40 ratio. The second guest (based on C89) is present at half occupancy and, as it also straddles a crystallographic inversion center, it is necessarily disordered with its symmetry related lattice equivalent. All solvent phenyl rings were treated as rigid hexagons, and ADP restraints were also included for the carbon atoms in the latter toluene moiety, to assist convergence. The pathway to the solution and refinement of compound 14 was impeded by a series of roadblocks. With a angle of close to 90 o, the data are credibly representative of orthorhombic symmetry. Indeed, the automated data reduction software suggested an R int of for a unit cell with mmm Laue symmetry wherein a, b, c,, and were, respectively, (5), (5), (5) Å, 90, 90 and 90 o. A variety of orthorhombic space groups were interrogated and the best of these afforded only minimal success for a very restrained and disordered model. On re-examining the raw data, it became evident that the correct symmetry, as presented here, is monoclinic, with twinning of almost 180 o about the 0,0,1 direction. The data were integrated using this twin law but the angle coupled with the twin angle did not afford good quality, de-convoluted data (probably because of the high degree of reflection overlap). Hence, the data were integrated in the monoclinic setting, as for a single crystal, and the twin law applied, post integration, in the refinement. Thus, the asymmetric unit was found to comprise 2 crystallographically independent molecules which each exhibit disorder of all Bpin atoms with the exception of the boron centres. The disorder ratios were determined to be 75:25 and 60:40 for the moieties based on B1 and B2, respectively. B-O, O-C and C-C distances involving fractional occupancy atoms were restrained to being similar in the final least-squares refinement cycles. ADP restraints were also employed in the disordered regions, on merit, to assist convergence. -S22-

23 Table S1: Single Crystal X-ray Data Parameters for compounds Compound Empirical formula C 204 H 280 B 4 Mg 4 N 8 O 12 C 61 H 73 BMgN 2 O 4 C 61 H 69 BMgN 2 O 4 C 90.5 H 136 B 2 Mg 2 N 6 O 6 C 48 H 70 BMgN 3 O 3 Formula weight Temperature/K (10) (10) (10) (10) (10) Crystal system monoclinic monoclinic monoclinic monoclinic monoclinic Space group P2 1 /c P2 1 /c P2 1 /n P2 1 /n P2 1 /n a/å (4) (19) (6) (10) (5) b/å (3) (14) (16) (3) (3) c/å (5) (2) (6) (8) (5) / β/ (3) (10) (6) (2) (2) / Volume/Å (2) (9) (5) (2) (3) Z ρ calc g/cm μ/mm F(000) Crystal size/mm Θ range for data collection/ to to to to Reflections collected Independent reflections 9229 [R int = , R sigma = ] [R int = , R sigma = ] [R int = , R sigma = ] [R int = , R sigma = ] to [R int = , R sigma = ] Data/restraints/parameters 9229/0/ /0/ /0/ /42/ /465/1180 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak/hole / e Å / / / / / S23-

24 Computational Details / Methodology DFT calculations were run with Gaussian 09 (Revision D.01). 3 The Mg center was described with the Stuttgart RECPs and associated basis sets, 4 and 6-31G** basis sets were used for all other atoms (BS1). 5 Initial BP86 6 optimizations were performed using the grid = ultrafine option, with all stationary points being fully characterized via analytical frequency calculations as minima (all positive eigenvalues). All energies were recomputed with a larger basis set (BS2) featuring G** on all atoms. Corrections for the effect of toluene (ε = ) solvent were run using the polarizable continuum model and BS1. 7 Single-point dispersion corrections to the BP86 results employed Grimme s D3 parameter set with Becke-Johnson damping as implemented in Gaussian. 8 References 1. Bourhis, L. J.; Dolomanov, O. V.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. Acta Cryst. A 2015, 71, Sheldrick, G. M. Acta Cryst. A, 2008, 64, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09 (Revision D.01); Gaussian Inc.: Wallingford, CT, Andrae, D., Ha ußermann, U., Dolg, M., Stoll, H., Preuß, H., Theor. Chim. Acta 1990, 77, (a) Hariharan, P. C., Pople, J. A. Theor. Chim. Acta 1973, 28, (b) Hehre, W. J., Ditchfield, R., Pople, J. A. J. Chem. Phys. 1972, 56, (a) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, (b) Perdew, J. P. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 33, Tomasi, J., Mennucci, B., Cammi, R. Chem. Rev. 2005, 105, S. Grimme, S. Ehrlich and L. Goerigk, Effect of the damping function in dispersion corrected density functional theory, J. Comp. Chem. 2011, 32, S24-

25 Breakdown of Energy Contributions The following tables detail the evolution of the relative energies as the successive corrections to the initial SCF energy are included. Terms used are: ΔE BS1 ΔH BS1 ΔG BS1 ΔG BS1/tol ΔG BS1/tol+D3 ΔG tol SCF energy computed with the BP86 functional with BS1 Enthalpy at 0 K with BS1 Free energy at K and 1 atm with BS1 Free energy corrected for toluene solvent with BS1 Free energy corrected for toluene and dispersion effects with BS1 Free energy corrected for basis set (BS2), dispersion effects and toluene solvent In each case the final data used in the main article is highlighted in bold. Energy Tables Table S2 Computed relative energies (kcal/mol) for the reactions of complexes 7, 10, 11, 12, 13 and 11. Data in bold are those used in the main text. All energies are quoted relative to 9 at 0.0 kcal/mol. ΔE BS1 ΔH BS1 ΔG BS1 ΔG BS1/tol ΔG BS1/tol+D3 ΔE BS2 ΔG tol ʹ S25-

26 Computed Energies (in Hartrees) n-bubpin SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = benzophone SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = fluorene SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = S26-

27 t-bunco SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = Dipp-NCO SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = ʹ SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = SCF (BP86) Energy = S27-

28 Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = SCF (BP86) Energy = Enthalpy 0K = Enthalpy 298K = Free Energy 298K = Lowest Frequency = cm -1 Second Frequency = cm -1 SCF (Toluene) Energy = SCF (BP86-D3BJ) Energy = SCF (BS2) Energy = S28-