Activation of a hydroamination gold catalyst by oxidation of a redox non-innocent chlorostibine Z-ligand

Transcription

1 Activation of a hydroamination gold catalyst by oxidation of a redox non-innocent chlorostibine Z-ligand Haifeng Yang and François P. Gabbaï Department of Chemistry, Texas A&M University, College Station, TX SUPPORTING INFORMATION This PDF file includes: Figure S1. 1 H, 31 P and 13 C spectra of 1-Cl and [1]SbF 6 in CDCl 3 Figure S2. 1 H and 31 P spectra of 2-Cl in CDCl 3 Figure S3. 1 H, 13 C, 31 P and 19 F spectra of 3-Cl in CDCl 3 Figure S4. 1 H, 13 C, 31 P and 19 F spectra of [3]SbF 6 in CDCl 3 Estimation of the Lewis acidity of cationic [(Ph 3 P) 2 Au]SbF 6 and [3]SbF 6 complexes by the Gutmann-Beckett method Figure S5. 31 P NMR spectra of CH 2 Cl 2 solutions (0.75 ml) containing the cationic gold complex (0.010 mmol) and tri(phenyl)phosphine oxide (0.011 mmol, 3.3 mg). General procedure for catalytic hydroamination reactions Figure S6. 1 H spectra for p-toluidine hydroamination of phenylacetylene Figure S7. 1 H spectra for 2,6-diisopropylaniline hydroamination of phenylacetylene. Figure S8. 1 H spectra for pentafluoroaniline hydroamination of phenylacetylene. Figure S9. 1 H spectra for phenylhydrazine hydroamination of phenylacetylene. Figure S10. 1 H NMR spectra for the hydroamination of 1-hexyne with p-toluidine. Table S1. Selected bond lengths (Å) and angles ( ) for complexes 1-Cl and [1] + as determined crystallographically and optimized computationally.

2 1 H NMR 1-Cl [1]SbF 6 31 P NMR 38.4 ppm 1-Cl [1]SbF ppm

3 13 CNMR 1-Cl [1]SbF 6 Figure S1. 1 H, 13 C and 31 P NMR spectra of 1-Cl and [1]SbF 6 in CDCl 3

4 1 H NMR 31 P NMR Figure S2. 1 H and 31 P spectra of 2-Cl in CDCl 3.

5 1 H NMR CH 2 Cl 2 13 CNMR

6 31 P NMR 19 FNMR Figure S3. 1 H, 13 C, 31 P and 19 Fspectra of 3-Cl in CDCl 3.

7 1 H NMR 13 C NMR

8 31 P NMR 19 F NMR Figure S4. 1 H, 13 C, 31 P and 19 F spectra of [3]SbF 6 in CDCl 3

9 Estimation of the Lewis acidity of cationic [(Ph 3 P) 2 Au]SbF 6 and [3]SbF 6 complexes by the Gutmann-Beckett method: 1 To a vial containing the desired gold complexes (0.010 mmol) was added CH 2 Cl 2 (500 µl). A 250 µl CH 2 Cl 2 slolution of triphenylphosphine oxide (0.011 mmol, 3.3 mg) was then slowly added the gold complex solutions. The reaction mixture was transferred to NMR tube. The chemical shift of the coordination complex was measured by 31 P NMR, and noted relative to triphenylphosphine oxide (27.30 ppm). 45.4ppm 45.4ppm 27.9 ppm 63.6 ppm 70.6 ppm 32.9 ppm

10 50.2 ppm Cl Sb Ph 2 P Au PPh 2 Cl 47.8ppm Ph 2 P Sb Au PPh 2 O PPh ppm Figure S5. 31 P NMR spectra of CH 2 Cl 2 solutions (0.75 ml) containing the cationic gold complex (0.010 mmol) and tri(phenyl)phosphine oxide (0.011 mmol, 3.3 mg).

11 General procedure for catalytic hydroamination reactions. Catalytic reactions were carried out in air. In a typical reaction, the alkyne (0.5 mmol) was mixed with the amine (0.55 mmol) in CDCl 3 (2 ml). After addition of the catalyst (3.5 mol% loading), conversion was estimated using 1 H NMR spectroscopy with 1,4-di-(tbutyl)benzene. Other reaction conditions including scaled-up reactions carried out for product isolation are described hereafter.

12 N-(1-phenylethylidene)-4-methylaniline N Yellow oil. Loading: phenylacetylene (2.5g, 24.5mmol), p-toluidine (2.5g, 23.4 mmol), catalyst (40mg, 0.3mol %). Reaction time 6 hr. Conversion 98%. Isolation: After evaporation of the solvent under vacuum, the product was extracted with pentane and purified by vacuum distillation. Isolated yield 92%. 1 Н NMR ( MHz; CDCl 3 ): δ = (m, 2Н), (m, 3Н), 7.18 (d, 3 J H H = 8.49, 2Н, Tol), 6.73 (d, 3 J H H = 8.49, 2Н, Tol), 2.38 (s, 3H, CH 3 ), 2.26 (s, 3H, CH 3 ). (b) Figure S6. 1 H NMR spectra for the hydroamination of phenylacetylene with p-toluidine. (a) 1 H NMR spectra collected for the purpose of reaction monitoring. (b) 1 H NMR spectrum of the isolated product.

13 2,6-diisopropyl-N-(1-phenylethylidene)aniline Light yellow solid, m.p Loading: phenylacetylene (276 mg, 2.7mmol), 2,6-diisopropylaniline (430 mg, 2.45 mmol), catalyst (9.0 mg, 0.3mol %). Reaction time 6hr. Conversion 93%. Isolation: After evaporation of the solvent under vacuum, the product was purified by recrystallization with ethanol and dried under vacuum. Isolated yield 83%. 1 Н NMR ( MHz; CDCl 3 ): δ = (m, 2H), (m, 3H), (m, 2H), (m, 1H), 2.78 (hept, J = 6.99 Hz, 2H), 2.14 (s, 3H), 1.17 (t, J = 6.99 Hz, 12H). (a) Without Cat. 0min CDCl 3 With Cat, 40 min With Cat, 70 min a b c d e f g (b) Figure S7. 1 H NMR spectra for the hydroamination of phenylacetylene with 2,6-diisopropylaniline. (a) 1 H NMR spectra collected for the purpose of reaction monitoring. (b) 1 H NMR spectrum of the isolated product.

14 2,3,4,5,6-pentafluoro-N-(1-phenylethylidene)aniline Loading: phenylacetylene (18.1mg, 0.18mmol), 2,3,4,5,6-pentafluoroaniline (29.2mg, 0.16 mmol). Reaction time 48h. NMR yield 68%. 1 Н NMR ( MHz; CDCl 3 ): δ = (m, 2H), (m, 3H), 2.33 (s, 3H). Without Cat. 0min With Cat, 16h With Cat, 42h With Cat, 48 h a b c Acetophenone Figure S8. 1 H NMR spectra for the hydroamination of phenylacetylene with pentafluoroaniline.

15 1-phenyl-2-(1-phenylethylidene)hydrazine Yellow solid, m.p Loading: phenylacetylene (168mg, 1.64mmol), phenylhydrazine (170mg, 1.57 mmol), catalyst (9.5 mg, 0.3mol %). Reaction time 2 hr. Conversion 86%. Isolation: After evaporation of the solvent under vacuum, the product was extracted with diethyl ether. After evaporation of the diethyl ether, the product was purified washed with methanol (2x 2mL) on a frit. Isolated yield 72%. 1 Н NMR ( MHz; CDCl 3 ): δ = (m, 2H), (m, 8H, ArH and NH), 6.91 (t, J = 6.99 Hz, 1H, p-ch of Ph), 2.26 (s, 3H, CH 3 ). (a) Without Cat. 0min With Cat, 20 min a b c-e g With Cat, 30 min f (b) Figure S9. 1 H NMR spectra for the hydroamination of phenylacetylene with phenylhydrazine. a) 1 H NMR spectra collected for the purpose of reaction monitoring. (b) 1 H NMR spectrum of the isolated product.

16 N-(hexan-2-ylidene)-4-methylaniline Loading: 1-hexyne (19.0mg, 0.23mmol), p-toluidine (24.8mg, 0.23 mmol), catalyst (9 mg, 3.4 mol%). Reaction time 60 min. NMR yield 61%. 1 Н NMR ( MHz; CDCl 3 ): δ = 7.10 (d, 2H), 6.60 (d, 2H), 2.32 (s, 3H, CH 3 ), 1.78 (s, 3H, CH 3 ), 1.66 (m, 2H, CH 2 ), 1.42 (m, 2H, CH 2 ), 1.22 (m, 2H, CH 2 ), 0.97 (t, 3H, CH 3 ). Without Cat. 0min With Cat, 60min a b c d e h f g Figure S10. 1 H NMR spectra for the hydroamination of 1-hexyne with p-toluidine. (1) Mewald, M.; Fröhlich, R.; Oestreich, M. Chem. Eur. J. 2011, 17,