Intermolecular Aminocarbonylation of Alkenes using Cycloadditions of Imino-Isocyanates. Supporting Information

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1 Intermolecular Aminocarbonylation of Alkenes using Cycloadditions of Imino-Isocyanates Amanda Bongers, Christian Clavette, Wei Gan, Serge I. Gorelsky, Lyanne Betit, Kaitlyn Lavergne, Thomas Markiewicz, Patrick J. Moon, Nicolas Das Neves, Nimrat K. Obhi, Amy B. Toderian, André M. Beauchemin* Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Contents Sciences, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada, K1N 6N5 Supporting Information 1. Intermolecular Aminocarbonylation of Alkenes... 2 Additional Optimization Data IR Study Computational Studies X-Ray Crystallography Ellipsoid Plots Spectra S1

2 1. Intermolecular Aminocarbonylation of Alkenes Additional Optimization Data Table S1. Survey of solvents for intermolecular aminocarbonylation of norbornene with first generation reagents a Entry Solvent BG = Ot-Bu (1f) 2f NMR Yield (%) b BG = OPh (1i) 2f NMR Yield (%) b 1 PhCF PhCl o-(cl2)c6h PhMe Pyridine Dioxane DMF t-buoh H2O neat 1 74 a Conditions: To a flame dried screw cap vial, 1 or 3 (0.2 mmol, 1 equiv) and norbornene (0.4 mmol, 2 equiv) in the solvent (1 ml). The reaction was heated at 90 ºC for 3 h. b NMR yields taken with 0.5 equiv of 1,3,5- trimethoxybenzene as an internal standard. Scheme S1. No reactivity has been achieved with various alkynes, copper (I) hexylacetylenide, or an allene. Scheme S2. No alkyne reactivity was observed with the non-planar imino-isocyanate precursor 1d. S2

3 2. IR Study (4) at 90 C Alkene added Product Figure S1. (a) Blue line=mixture of 4 in toluene at 90 C after 10 min. Red line = Analysis after norbornene added. Pink line =spectrum of azomethine imine 5a product in toluene. (b) Blue spectrum in closer detail. Procedure: Hydrazone 4 in toluene (0.05 M) was heated at 90 C, and the mixture became a yellow solution which then became dark ruby red. After 10 min, analysis of the sample showed a peak appeared at 2191 cm -1, corresponding to the asymmetric NCO stretch of the iminoisocyanate. This peak does not match the expected frequency of the azine ( cm -1 ). 1 After the 20 minutes, norbornene was added to the reaction mixture. The ruby colour immediately disappeared, and the mixture returned to a pale yellow solution. Prompt analysis of the reaction mixture revealed no peak at 2191 cm Frederickson, L. D. Anal. Chem. 1964, 36, S3

4 3. Computational Studies Density functional theory (DFT) calculations have been performed using the Gaussian 09 software package, 2 as described in our prior communication. 3 Optimized molecular geometries were calculated using the B3LYP exchange-correlation functional in vacuum and in methanol solution. 4 For the latter, the SMD implicit solvation model was used with the default solvent parameters. 5 The triple-zeta TZVP basis set and tight SCF convergence criteria were used for all calculations. 6 Wave function stability calculations were performed to confirm that the calculated wave functions corresponded to the ground state. Harmonic frequency calculations were performed to ensure that the stationary points were true energy minima or transition states The unscaled frequencies were used for calculating the Gibbs free energies of the species at 298 K and 1 atm. Intrinsic reaction coordinate (IRC) calculations were used to confirm the reaction pathways through the transition states for all reported reactions. 7 2 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 Jr., J. A.; 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, N. J.; 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, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02; Gaussian, Inc., Wallingford, CT, Clavette, C.; Gan, W.; Bongers, A.; Markiewicz, T.; Toderian, A. B.; Gorelsky, S. I.; Beauchemin, A. M. J. Am. Chem. Soc. 2012, 134, a) Becke, A. D. J. Chem. Phys. 1993, 98, b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, a) Schafer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, b) Gonzalez, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, Gonzalez, C.; Schlegel, H. B. J. Phys. Chem. 1990, 94, S4

5 Optimized Cartesian coordinates (Å), electronic and Gibbs free energies (au), and energies of highest occupied and lowest unoccupied molecular orbitals (ev) CH3OH in vacuum E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C H H H O H CH3OH in liquid methanol E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C H H H O H Reactant in vacuum E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C H C H N C H H H H C O O C H H H N H S5

6 Reactant in liquid metanol E(SCF)= au, G= a.u. ε(homo)= ev, ε(lumo)= ev C H C H N C H H H H C O O C H H H N H Isocyanate intermediate in vacuum E(SCF)= au, G= au ε(homo)= ε(lumo)= ev C H C H N N C O C H H H H S6

7 Isocyanate intermediate in liquid methanol E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C H C H N N C O C H H H H Norbornene in vacuum E= au, G= au ε(homo)= ev, ε(lumo)= ev C C C C H H H H C H H H H C C H H S7

8 Norbornene in liquid methanol E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C C C C H H H H C H H H H C C H H Transition state with norbornene in vacuum, one imaginary frequency at i307 cm -1 E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C C C C H H H H C H H H H C C H H C H C H N S8

9 N C O C H H H H Transition state with norbornene in liquid methanol, one imaginary frequency at i313 cm -1 E= au, G= au ε(homo)= ev, ε(lumo)= ev C C C C H H H H C H H H H C C H H C H C H N N C O C H H H H S9

10 Product with norbornene in vacuum E= au, G= au ε(homo)= ev, ε(lumo)= ev C C C C H H H H C H H H H C C H H C H C H N N C O C H H H H Product with norbornene in liquid methanol E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= -751 ev C C C C H H H H C S10

11 H H H H C C H H C H C H N N C O C H H H H C2H4 in vacuum E= au, G= au ε(homo)= ev, ε(lumo)= ev C H H C H H Transition state with C2H4 in vacuum, one imaginary frequency at i370 cm -1 E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C H H C H H C H C H N S11

12 N C O C H H H H Product with C2H4 in vacuum E(SCF)= au, G= au ε(homo)= ev, ε(lumo)= ev C H H C H H C H C H N N C O C H H H H S12

13 4. X-Ray Crystallography Ellipsoid Plots Figure S2. Ellipsoid plot and acquisition data for compound 2f. The raw data (cif file) is available at S13

14 Figure S3. Ellipsoid plot and acquisition data for compound 3f. The raw data (cif file) is available at S14

15 Figure S4. Ellipsoid plot and acquisition data for compound 5a. The raw data (cif file) is available at S15

16 Figure S5. Ellipsoid plot and acquisition data for compound 5r. The raw data (cif file) is available as Supporting Information for this article. S16

17 Figure S6. Ellipsoid plot and acquisition data for compound 5ab. The raw data (cif file) is available as Supporting Information for this article. S17

18 Figure S7. Ellipsoid plot and acquisition data for compound 12j. The raw data (cif file) is available as Supporting Information for this article. S18

19 Figure S8. Ellipsoid plot and acquisition data for compound 18. The raw data (cif file) is available at S19

20 Figure S9. Ellipsoid plot and acquisition data for compound 20a. The raw data (cif file) is available at S20

21 5. Spectra S21

22 h S22

23 i S23

24 k S24

25 l S25

26 m S26

27 S27

28 F NMR S28

29 S29

30 o S30

31 p S31

32 q S32

33 s S33

34 t S34

35 5v S35

36 w S36

37 y S37

38 z S38

39 c S39

40 a S40

41 11a S41

42 11b S42

43 11c S43

44 11d S44

45 11e S45

46 b S46

47 17c S47

48 S48 19b

49 S49 13c

50 20b S50

51 20c S51

52 20d S52

53 20e S53

54 20f S54