Supporting Information. Lithium Cadmate-Mediated Deprotonative Metalation of Anisole: Experimental and Computational Study

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1 Supporting Information Lithium Cadmate-Mediated Deprotonative Metalation of Anisole: Experimental and Computational Study Katia Snégaroff, Shinsuke Komagawa, Mitsuhiro Yonehara, Floris Chevallier, Philippe C. Gros, Masanobu Uchiyama*, and Florence Mongin*, Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, Rennes, France The Institute of Physical and Chemical Research, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama , Japan SOR, SRSMC, CNRS, Université de Nancy, Boulevard des Aiguillettes, Vandœuvre-Lès-Nancy, France Table of Contents 1. General Procedures S-2 2. Experimental Procedures S-2 3. Computational Methods S-3 4. Cartesian Coordinates and Total Electron Energies S-4 S-1

2 General Procedures: The reactions were performed in Schlenk tubes under argon atmosphere. THF was freshly distilled over sodium/benzophenone. Liquid chromatography separations were achieved on silica gel Merck Geduran Si 60 ( μm). CdCl 2 TMEDA was prepared as described previously, 1 by adapting a known procedure. 2 1 H and 13 C-Nuclear magnetic resonance (NMR) spectra were recorded at 300 and 75 MHz, respectively. The procedure used to deprotonate anisole and the data concerning 2-iodoanisole have been previously described. 3 Experimental Procedures: (TMP) 3 CdLi, (P) 3 CdLi, (HMDS) 3 CdLi, (DA) 3 CdLi, (P)Cd(TMP) 2 Li, (HMDS)Cd(TMP) 2 Li, (TMP)Cd(HMDS) 2 Li, (DA)Cd(TMP) 2 Li and (TMP)Cd(DA) 2 Li: To a stirred, cooled (0 C) solution of the required secondary amine(s) (6.0 mmol) in THF (5 ml) was successively added BuLi (about 1.6 M hexanes solution, 6.0 mmol) and, 15 min later, CdCl 2 TMEDA (0.60 g, 2.0 mmol). The mixture was stirred for 15 min at 0 C. BuCd(TMP) 2 Li, s BuCd(TMP) 2 Li, t BuCd(TMP) 2 Li and TMSCH 2 Cd(TMP) 2 Li: To a stirred, cooled (0 C) solution of 2,2,6,6-tetramethylpiperidine (0.68 ml, 4.0 mmol) in THF (5 ml) was added BuLi (about 1.6 M hexanes solution, 4.0 mmol). After 15 min at 0 C, CdCl 2 TMEDA (0.60 g, 2.0 mmol) was added, and the mixture was stirred for 15 min at this temperature before addition of the required alkyllithium (2.0 mmol). The mixture was stirred for further 15 min at 0 C. Bu 2 Cd(TMP)Li, s Bu 2 Cd(TMP)Li, t Bu 2 Cd(TMP)Li and (TMSCH 2 ) 2 Cd(TMP)Li: To a stirred, cooled (0 C) solution of 2,2,6,6-tetramethylpiperidine (0.34 ml, 2.0 mmol) in THF (5 ml) was added BuLi (about 1.6 M hexanes solution, 2.0 mmol). After 15 min at 0 C, CdCl 2 TMEDA (0.60 g, 2.0 mmol) was added, and the mixture was stirred for 15 min at this temperature before addition of the required alkyllithium (4.0 mmol). The mixture was stirred for further 15 min at 0 C. 1 Snégaroff, K.; L'Helgoual'ch, J.-M.; Bentabed-Ababsa, G.; Nguyen, T. T.; Chevallier, F.; Yonehara, M.; Uchiyama, M.; Derdour, A.; Mongin, F. Chem. Eur. J. 2009, 15, Kedarnath, G.; Kumbhare, L. B.; Jain, V. K.; Phadnis, P. P.; Nethaji, M. Dalton Trans. 2006, L'Helgoual'ch, J.-M.; Bentabed-Ababsa, G.; Chevallier, F.; Yonehara, M.; Uchiyama, M.; Derdour, A.; Mongin, F. Chem. Commun. 2008, S-2

3 Bu 3 CdLi and (TMSCH 2 ) 3 CdLi: To a stirred, cooled (0 C) solution of CdCl 2 TMEDA (0.60 g, 2.0 mmol) in THF (5 ml) was added the required alkyllithium (6.0 mmol). The mixture was stirred for 15 min at 0 C. Computational Methods: All calculations were carried with the Gaussian 03 program package. 4 The molecular structures and harmonic vibrational frequencies were obtained using the hybrid density functional method based on Becke's three parameter exchange function and the Lee Yang Parr nonlocal correlation functional (B3LYP). 5 We used Ahlrichs' SVP all electron basis set 6 for the zinc atom and 6 31G* for the other atoms (denoted as 631SVPs in the text). Geometry optimization and vibrational analysis were performed at the same level. All stationary points were optimized without any symmetry assumptions, and characterized by normal coordinate analysis at the same level of theory (number of imaginary frequencies, NIMAG, 0 for minima and 1 for TSs). The intrinsic reaction coordinate (IRC) method 7 was used to track minimum energy paths from transition structures to the corresponding local minima. The calculations were performed by using the RIKEN Cluster of Clusters (RICC) facility. 4 Gaussian 03, Revision E.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; 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.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc., Wallingford CT, (a) Becke, A. D. Phys. Rev. 1988, A38, (b) Becke, A. D. J. Chem. Phys. 1993, 98, (c) Becke, A. D. J. Chem. Phys. 1993, 98, (d) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, (a) Fukui, K. Acc. Chem. Res. 1981, 14, (b) Gonzalez, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, (c) Gonzalez, C.; Schlegel, H. B. J. Chem. Phys. 1990, 94, S-3

4 Cartesian Coordinates and Total Electron Energies Anisole (RT) SCF Done: E(RB+HF-LYP) = A.U (NMe 2 ) 3 CdLi-Me 2 O (RT1) SCF Done: E(RB+HF-LYP) = A.U S-4

5 MeCd(μ-NMe 2 ) 2 Li-Me 2 O (RT2) SCF Done: E(RB+HF-LYP) = A.U S-5

6 (NMe 2 )Cd(μ-NMe 2 )(μ-me)li-me 2 O (RT3) SCF Done: E(RB+HF-LYP) = A.U MeCd(μ-NMe 2 )(μ-me)li-me 2 O (RT4) SCF Done: E(RB+HF-LYP) = A.U S-6

7 (NMe 2 )Cd(μ-Me) 2 Li-Me 2 O (RT5) SCF Done: E(RB+HF-LYP) = S-7

8 IM1 SCF Done: E(RB+HF-LYP) = A.U S-8

9 IM2 SCF Done: E(RB+HF-LYP) = A.U S-9

10 IM3 SCF Done: E(RB+HF-LYP) = A.U S-10

11 IM4 SCF Done: E(RB+HF-LYP) = A.U S-11

12 IM5 SCF Done: E(RB+HF-LYP) = A.U S-12

13 IM6 SCF Done: E(RB+HF-LYP) = A.U S-13

14 IM7 SCF Done: E(RB+HF-LYP) = A.U TS1 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U. S-14

15 S-15

16 TS2 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U S-16

17 TS3 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U S-17

18 TS4 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U S-18

19 TS5 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U S-19

20 TS6 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U S-20

21 TS7 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U TS8 Imaginary frequencies: SCF Done: E(RB+HF-LYP) = A.U. S-21

22 PD1 SCF Done: E(RB+HF-LYP) = A.U S-22

23 PD2 SCF Done: E(RB+HF-LYP) = A.U. S-23

24 S-24

25 PD3 SCF Done: E(RB+HF-LYP) = A.U S-25

26 PD4 SCF Done: E(RB+HF-LYP) = A.U S-26

27 PD5 SCF Done: E(RB+HF-LYP) = A.U S-27

28 PD6 SCF Done: E(RB+HF-LYP) = A.U PD7 SCF Done: E(RB+HF-LYP) = A.U. S-28

29 S-29