Supporting Information
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2015
Cationic Zinc Organyls as Precatalysts for Hydroamination
Reactions
Maren A. Chilleck,[a] Larissa Hartenstein,[b] Thomas Braun,*[a] Peter W. Roesky,*[b] and
Beatrice Braun[a]
chem_201405662_sm_miscellaneous_information.pdf
Supporting Information
Figure S1. Time-dependent conversion of the hydroamination reaction of phenylacetylene with 2,4,6trimethylaniline catalyzed by [Zn2Cp*3]+[BArF4]− (2). Reaction conditions: 2 (2.5 mol%, 0.014 mmol), 2,4,6trimethylaniline (40 eq, 0.57 mmol), phenylacetylene (40 eq, 0.57 mmol), 1,2-difluorobenzene (0.5 mL), rt.
The conversion was determined by 1H NMR spectroscopy.
Figure S2. 1H NMR spectrum (400.1 MHz, C6D6, 298 K) of (Cp*)(Ph)CCH2 (4). The smaller unmarked
signals are due to unidentified impurities.
Figure S3. 13C{1H} NMR spectrum (100.6 MHz, C6D6, 298 K) of (Cp*)(Ph)CCH2 (4).
Figure S4. 1H NMR spectrum (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of [ZnEt(2,4,6Me3C6H2NH2)3]+[BArF4]− (5), low field region.
Figure S5. 1H NMR spectrum (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of [ZnEt(2,4,6Me3C6H2NH2)3]+[BArF4]− (5), high field region.
Figure S6. 13C{1H} NMR spectrum (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of [ZnEt(2,4,6Me3C6H2NH2)3]+[BArF4]− (5), low field region.
Figure S7. 13C{1H} NMR spectrum (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of [ZnEt(2,4,6Me3C6H2NH2)3]+[BArF4]− (5), high field region.
Figure S8. 1H NMR spectrum (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of [ZnEt(C6H5NH2)3]+[BArF4]−
(6), low field region.
Figure S9. 1H NMR spectrum (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of [ZnEt(C6H5NH2)3]+[BArF4]−
(6), high field region. The signal at δ=0.66 ppm is ascribed to ethane, which is probably formed by reaction
with traces of water.
Figure S10. 13C{1H} NMR spectrum (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of
[ZnEt(C6H5NH2)3]+[BArF4]− (6), low field region.
Figure S11. 13C{1H} NMR spectrum (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K) of
[ZnEt(C6H5NH2)3]+[BArF4]− (6), high field region.
NMR Data of Hydroamination Products
Intramolecular Hydroamination
The substrates 2,2-diphenyl-pent-4-enylamine,[1] C-(1-allyl-cyclohexyl)-methylamine,[1] 1-amino2,2-diphenylhex-5-ene,[2] 5-phenylpent-4-yn-1-amine,[3] and (4E)-2,2-dimethyl-5-phenylpent-4enylamine[1] were synthesized according to the literature procedures.
The 1H NMR spectra of 2-methyl-4,4-diphenylpyrrolidine,[1] 3-methyl-2-aza-spiro-[4.5]decane,[1]
2-methyl-5,5-diphenylpiperidine,[2] and 2-benzyl-1-pyrroline[3] conform with the literature.
Intermolecular Hydroamination
The following NMR and GC/MS data were determined employing the reaction mixtures of the
hydroamination experiments. Due to signal overlap of the product resonances with the
resonances of the solvent 1,2-difluorobenzene and the starting materials in the aromatic regions
of the NMR spectra, only the signals in the aliphatic regions are given.
N-(1-(p-methoxyphenyl)ethylidene)-2,4,6-trimethylaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.56 (s, 3H; OMe), 2.11 (s, 3H; CH3), 1.85 (s,
6H; CH3), 1.82 ppm (s, 3H; CH3); 13C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.4
(OMe), 20.1 (CH3), 17.4 (CH3), 16.3 ppm (CH3); GC/MS (70 eV): m/z: 267 [M+], 252 [M+ − CH3], 237 [M+ −
2 CH3].
N-(1-(p-chlorophenyl)ethylidene)-2,4,6-trimethylaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=2.10 (s, 3H; CH3), 1.82 (s, 6H; CH3), 1.79 ppm
(s, 3H; CH3); 13C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=20.1 (s; CH3), 17.3 (s; CH3),
16.2 ppm (s, br; CH3); GC/MS (70 eV): m/z: 271 [M+], 256 [M+ − CH3], 241 [M+ − 2 CH3], 91 [C7H7+].
N-(1-(p-fluorophenyl)ethylidene)-2,4,6-trimethylaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=2.11 (s, 3H; CH3), 1.83 (s, 6H; CH3), 1.81 ppm
(s, 3H; CH3); 13C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=20.1 (s; CH3), 17.3 (s; CH3),
16.3 ppm (s, br; CH3); 19F NMR (282.4 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=−111.9 ppm (s);
GC/MS (70 eV): m/z: 255 [M+], 240 [M+ − CH3], 225 [M+ − 2 CH3].
N-(1-phenylethylidene)aniline
1
H NMR (500.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.95 ppm (s, 3H; CH3); 13C{1H} NMR
(125.8 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.4 ppm (CH3); GC/MS (70 eV): m/z: 195 [M+], 180
[M+ − CH3], 77 [C6H5+].
N-(1-(p-methoxyphenyl)ethylidene)aniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.54 (s, 3H; OMe), 1.95 ppm (s, 3H; CH3);
C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.4 (OMe), 16.1 ppm (CH3); GC/MS
(70 eV): m/z: 225 [M+], 210 [M+ − CH3], 77 [C6H5+].
13
N-(1-(p-chlorophenyl)ethylidene)aniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.92 ppm (s, 3H; CH3); 13C{1H} NMR
(100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.1 ppm (CH3); GC/MS (70 eV): m/z: 229 [M+], 214
[M+ − CH3], 77 [C6H5+].
N-(1-(p-fluorophenyl)ethylidene)aniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.92 ppm (s, 3H; CH3); 13C{1H} NMR
(100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.1 ppm (CH3); 19F NMR (282.4 MHz, 1,2-F2C6H4,
C6D6 capillary, 298 K): δ=−111.5 ppm (m); GC/MS (70 eV): m/z: 213 [M+], 198 [M+ − CH3], 77 [C6H5+].
N-(1-phenylethylidene)-p-methoxyaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.52 (s, 3H; OMe), 2.01 ppm (s, 3H; CH3);
C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.5 (OMe), 16.3 ppm (CH3); GC/MS
(70 eV): m/z: 225 [M+], 210 [M+ − CH3].
13
N-(1-(p-methoxyphenyl)ethylidene)-p-methoxyaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.54 (s, 3H; OMe), 3.53 (s, 3H; OMe),
2.01 ppm (s, 3H; CH3); 13C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.5 (OMe), 54.4
(OMe), 16.0 ppm (CH3); GC/MS (70 eV): m/z: 255 [M+], 240 [M+ − CH3].
N-(1-(p-chlorophenyl)ethylidene)-p-methoxyaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.53 (s, 3H; OMe), 1.98 ppm (s, 3H; CH3);
C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.5 (OMe), 16.0 ppm (CH3); GC/MS
(70 eV): m/z: 259 [M+], 244 [M+ − CH3].
13
N-(1-(p-fluorophenyl)ethylidene)-p-methoxyaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.53 (s, 3H; OMe), 1.98 ppm (s, 3H; CH3);
C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.5 (OMe), 16.1 ppm (CH3); 19F NMR
(282.4 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=−111.9 ppm (m); GC/MS (70 eV): m/z: 243 [M+], 228
[M+ − CH3].
13
N-(1-phenylethylidene)-p-chloroaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.94 ppm (s, 3H; CH3); 13C{1H} NMR
(100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.3 ppm (CH3); GC/MS (70 eV): m/z: 229 [M+], 214
[M+ − CH3], 111 [C6H4Cl+].
N-(1-(p-methoxyphenyl)ethylidene)-p-chloroaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.55 (s, 3H; OMe), 1.94 ppm (s, 3H; CH3);
C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.4 (OMe), 16.0 ppm (CH3); GC/MS
(70 eV): m/z: 259 [M+], 244 [M+ − CH3], 111 [C6H4Cl+].
13
N-(1-(p-chlorophenyl)ethylidene)-p-chloroaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.92 ppm (s, 3H; CH3); 13C{1H} NMR
(100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.1 ppm (CH3); GC/MS (70 eV): m/z: 263 [M+], 248
[M+ − CH3], 111 [C6H4Cl+].
N-(1-(p-fluorophenyl)ethylidene)-p-chloroaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.92 ppm (s, 3H; CH3); 13C{1H} NMR
(100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.1 ppm (CH3); 19F NMR (282.4 MHz, 1,2-F2C6H4,
C6D6 capillary, 298 K): δ=−111.2 ppm (s); GC/MS (70 eV): m/z: 247 [M+], 232 [M+ − CH3], 111 [C6H4Cl+].
N-(1-phenylethylidene)-p-fluoroaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.95 ppm (s, 3H; CH3); 13C{1H} NMR
(100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.2 ppm (CH3); 19F NMR (282.4 MHz, 1,2-F2C6H4,
C6D6 capillary, 298 K): δ=−122.1 ppm (s); GC/MS (70 eV): m/z: 213 [M+], 198 [M+ − CH3], 95 [C6H4F+].
N-(1-(p-methoxyphenyl)ethylidene)-p-fluoroaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=3.55 (s, 3H; OMe), 1.96 ppm (s, 3H; CH3);
C{1H} NMR (100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=54.4 (OMe), 16.0 ppm (CH3); 19F NMR
(282.4 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=−122.5 ppm (s); GC/MS (70 eV): m/z: 243 [M+], 228 [M+
− CH3], 95 [C6H4F+].
13
N-(1-(p-chlorophenyl)ethylidene)-p-fluoroaniline
1
H NMR (500.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.93 ppm (s, 3H; CH3); 13C{1H} NMR
(125.8 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.0 ppm (CH3); 19F NMR (470.6 MHz, 1,2-F2C6H4,
C6D6 capillary, 298 K): δ=−121.8 ppm (s); GC/MS (70 eV): m/z: 247 [M+], 232 [M+ − CH3], 95 [C6H4F+].
N-(1-(p-fluorophenyl)ethylidene)-p-fluoroaniline
1
H NMR (400.1 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=1.94 ppm (s, 3H; CH3); 13C{1H} NMR
(100.6 MHz, 1,2-F2C6H4, C6D6 capillary, 298 K): δ=16.0 ppm (CH3); 19F NMR (282.4 MHz, 1,2-F2C6H4,
C6D6 capillary, 298 K): δ=−111.5 (s), −122.0 ppm (s); GC/MS (70 eV): m/z: 231 [M+], 216 [M+ − CH3], 95
[C6H4F+].
References
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Soc. 2009, 131, 9670–9685.
[3] Y. Li, T. J. Marks, J. Am. Chem. Soc. 1996, 118, 9295–9306.