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The Ti-BINOLate-Catalyzed, Enantioselective Ring-Opening of meso-Aziridines with Amines
Saravanan Peruncheralathana, Sandra Aurich
a, Henrik Teller
a and Christoph Schneider*
a
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
Supplementary Material
Detailed Information about ESI-MS analysis of the formed BINOL/Ti complexes ........................................ 2
BINOL as ligand ................................................................................................................................................................... 2
Bridged bis-BINOL 11 as ligand ........................................................................................................................................... 3
Experimental Data of new compounds/Compounds synthesized by a new method ........................................ 4
(1S,2S)-N-(4-Chlorophenyl)-N’-phenylcyclohexane-1,2-diamine (3e) .................................................................................. 4
(1S,2S)-N-(Phenyl)-N’-(4-trifluoromethylphenyl)-cyclohexane-1,2-diamine (3g) ................................................................ 5
(1S,2S)-N-(4-Cyanophenyl)-N’-phenylcyclohexane-1,2-diamine (3h) .................................................................................. 6
(1S,2S)-N-(4-Carbomethoxyphenyl)-N’-phenylcyclohexane-1,2-diamine (3i) ...................................................................... 7
4-((1S,2S)-2-(Phenylamino)cyclohexylamino)benzenethiol (3k) .......................................................................................... 8
(1S,2S)-N-Phenyl-N’-m-tolylcyclohexane-1,2-diamine (3l) .................................................................................................. 9
(1S,2S)-N-(3-Methoxyphenyl)-N’-phenylcyclohexane-1,2-diamine (3m) ........................................................................... 10
(1S,2S)-N-(3-Bromophenyl)-N’-phenylcyclohexane-1,2-diamine (3n) ............................................................................... 11
(1S,2S)-N-Phenyl-N’-(3-trifluoromethylphenyl)cyclohexane-1,2-diamine (3o) .................................................................. 12
(1S,2S)-N-Phenyl-N’-o-tolylcyclohexane-1,2-diamine (3p) ................................................................................................ 13
(1S,2S)-N-(2-Methoxyphenyl)-N’-phenylcyclohexane-1,2-diamine (3q) ............................................................................ 13
(1S,2S)-N-(2-Flurophenyl)-N’-phenylcyclohexane-1,2-diamine (3r) .................................................................................. 14
(1S,2S)-N-(2-Carbomethoxyphenyl)-N’-phenylcyclohexane-1,2-diamine (3s) ................................................................... 15
(1S,2S)-N-(1-Naphthyl)-N'-phenylcyclohexane-1,2-diamine (3t) ........................................................................................ 16
(1S,2S)-N-(2,4-Diflurophenyl)-N’-phenylcyclohexane-1,2-diamine (3u) ............................................................................ 17
(1S,2S)-N-(3,4-Dimethoxyphenyl)-N’-phenylcyclohexane-1,2-diamine (3v) ...................................................................... 18
(1S,2S)-N-Phenyl-N’-(3,4,5-trimethoxyphenyl)cyclohexane-1,2-diamine (3w) .................................................................. 19
(1S,1’S,2S,2’S)-N1,N1’-(1,4-Phenylene)bis(N2-phenylcyclohexane-1,2-diamine) (3x) ........................................................ 20
4-((1S,2S)-2-(Phenylamino)cyclopentylamino)benzenethiol (4e) ....................................................................................... 21
(1S,2S)-N-(2-Methoxyphenyl)-N’-phenylcyclopentan-1,2-diamine (4f) .............................................................................. 22
(2S,3S)-N2,N3-Diphenyl-1,2,3,4-tetrahydronaphthalen-2,3-diamine (6a) ............................................................................ 22
4-[(2S,3S)-3-(phenylamino)butan-2-ylamino]benzenethiol (7b) ......................................................................................... 23
(1R,3S,4S,6S)-N,N’-Diphenyl-7-tosyl-7-azabicyclo[4.1.0]-heptane-3,4-diamine (8a) ......................................................... 24
(3S,4S)-N,N’-Diphenyltetrahydrofuran-3,4-diamine (9a) .................................................................................................... 25
(5S,6S)-2,2-Dimethyl-N,N’-diphenyl-1,3-dioxepan-5,6-diamine (10a) ............................................................................... 25
(5S,6S)-Methyl-4-((-2,2-dimethyl-6-(phenylamino)-1,3-dioxepan-5-yl)amino)benzoate (10b) .......................................... 26
(5S,6S)-4-(2,2-Dimethyl-6-(phenylamino)-1,3-dioxepan-5-yl)aS. 26mino)benzonitrile (10c) ............................................ 27
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
2
Detailed Information about ESI-MS analysis of the formed BINOL/Ti complexes
High resolution ESI mass spectra for the analysis of BINOL/Ti complexes were recorded on a Brucker APEX II
FT-ICR, the low resolution ESI-MS/MS spectra were recorded on an ESQUIRE 3000 Plus (Bruker Daltonics).
Because of the special isotopic pattern of such complexes with often more than 100 carbon atoms and some
titanium atoms, the calculated exact mass often differs from the observed maximum of the signal with ∆m = 1.
This is in agreement with the calculated isotopic pattern.
BINOL as ligand
ESI-MS-experiments were carried out with a mixture of Ti(OtBu)4, (R)-BINOL and aniline (1:2.2:10) in CH2Cl2,
which had been prepared according to the general synthetic protocol.
Table 1 Results with CH2Cl2 as solvent
Species Molecular formular m/z (calcd.) m/z (found) ∆ppm
[5 BINOL + 3 Ti + O + H]+ C100H61O11Ti3 1581.26523 1581.27209 4
[6 BINOL + 4 Ti + 2 O + 2 H2O + H]+ C120H77O16Ti4 1965.31240 1965.31907 3
Table 2 Additional Species with CH2Cl2/MeCN as solvent
Species Molecular formular m/z (calcd.) m/z (found) ∆ppm
[6 BINOL + 3 Ti + H]+ C120H73O12Ti3 1849.35350 1849.36931 8
Table 3 Results after addition of 10 eq. aziridine 1a in CH2Cl2
Species Molecular formular m/z (calcd.) m/z (found) ∆ppm
[6 BINOL + 4 Ti + 4 H2O + 3 aziridine +
3 aniline]+
C174H143N6O16Ti4 2764.84730 2764.81534 11
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
3
Bridged bis-BINOL 11 as ligand
ESI-MS-experiments were carried out with a mixture of Ti(OtBu)4, the linked bis-BINOL ligand 11 and aniline
(1:1.1:10) in CH2Cl2 which had been prepared according to the general synthetic protocol.
Table 4 Results with CH2Cl2 as solvent
Species Molecular formular m/z (calcd.) m/z (found) ∆ppm
[2 11 + 2 Ti + H2O - H]- C84H3O11Ti2 1333.25523 1333.25118 3
Table 5 Additional Species with CH2Cl2/MeCN as solvent
Species Molecular formular m/z (calcd.) m/z (found) ∆ppm
[11 + Ti + H]+ C42H27O5Ti 659.1338 659.13666 4
[2 11 + 2 Ti + H]+ C84H53O10Ti2 1317.25977 1317.26233 2
[2 11 + 2 Ti + H2O + H]+ C84H55O11Ti2 1335.2703 1335.27083 0,4
[3 11 + 3 Ti + H2O + H]+ C126H81O16Ti3 1994.3963 1994.43480 19a
a higher aberration between calculated und found m/z because of measuring at the detection limit.
Table 6 Results after addition of 10 eq. aziridine 1a in CH2Cl2
Species Molecular formular m/z (calcd.) m/z (found) ∆ppm
[2 11 + 2 Ti + aziridine + aniline + H]+ C102H75N2O10Ti2 1583.4381 1583.43296 3
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
Experimental Data of new compounds/Compounds synthesized by a new method
(1S,2S)-N
Experimental Data of new compounds/Compounds synthesized by a new method
N-(4-Chlorophenyl)
Experimental Data of new compounds/Compounds synthesized by a new method
Chlorophenyl)-N’-phenylcyclohexane
Experimental Data of new compounds/Compounds synthesized by a new method
phenylcyclohexane-1,2
4
Experimental Data of new compounds/Compounds synthesized by a new method
1,2-diamine (3e)
Experimental Data of new compounds/Compounds synthesized by a new method
diamine (3e)
Experimental Data of new compounds/Compounds synthesized by a new methodExperimental Data of new compounds/Compounds synthesized by a new methodExperimental Data of new compounds/Compounds synthesized by a new method
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-(Phenyl)-N’-(4(4-trifluoromethylphenyl)
trifluoromethylphenyl)-cyclohexane
5
cyclohexane-1,2--diamine (3g)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
6
(1S,2S)-N-(4-Cyanophenyl)-N’-phenylcyclohexane-1,2-diamine (3h)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.56.66.76.87.17.27.37.4f1 (ppm)
0102030405060708090100110120130140150160170f1 (ppm)
24.52
24.72
32.28
32.64
57.02
57.13
76.83
77.15
77.47
98.81
112.77
113.53
117.98
120.52
129.54
133.81
147.36
151.03
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
7
(1S,2S)-N-(4-Carbomethoxyphenyl)-N’-phenylcyclohexane-1,2-diamine (3i)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.56.66.76.87.17.27.37.87.9f1 (ppm)
0102030405060708090100110120130140150160170180f1 (ppm)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
4-((1S,2S)
)-2-(Phenylamino)(Phenylamino)cyclohexylamino)cyclohexylamino)benzenethiol (3k
8
benzenethiol (3k)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-Phenyl-N’-m--tolylcyclohexane
tolylcyclohexane-1,2-diamine (3l)
9
diamine (3l)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
10
(1S,2S)-N-(3-Methoxyphenyl)-N’-phenylcyclohexane-1,2-diamine (3m)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
6.26.36.66.76.87.17.27.3f1 (ppm)
0102030405060708090100110120130140150160170f1 (ppm)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-(3-Bromophenyl)Bromophenyl)-N’-phenylcyclohexane
phenylcyclohexane-1,2
11
1,2-diamine (3n)diamine (3n)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-Phenyl-N’-(3--trifluoromethylphenyl)cyclohexane
trifluoromethylphenyl)cyclohexane
12
trifluoromethylphenyl)cyclohexane-1,2-diamine (3o)diamine (3o)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
(1S,2S)-N
8.0
7.2
N-Phenyl-N’-o-tolylcyclohexane
N-(2-Methoxyphenyl)
7.07.5
6.9f1 (ppm)
tolylcyclohexane
Methoxyphenyl)-N’-phenylcyclohexane
6.06.5
6.76.8f1 (ppm)
tolylcyclohexane-1,2-diamine (3p)
phenylcyclohexane
5.05.5
6.6 2.42.5f1 (ppm)
13
diamine (3p)
phenylcyclohexane-1,2-diamine
3.54.04.5f1 (ppm)
2.32.4f1 (ppm)
diamine (3q)
2.53.03.5
1.9
1.52.02.5
1.51.8f1 (ppm)
0.51.01.5
1.31.41.5f1 (ppm)
0.0
1.2
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-(2-Flurophenyl)Flurophenyl)-N’-phenylcyclohexanephenylcyclohexane-1,2
14
,2-diamine (3r)(3r)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
8.59.0
N-(2-Carbomethoxyphenyl)
7.58.08.5
7.47.87.9
Carbomethoxyphenyl)-N
6.57.0
7.17.27.37.4f1 (ppm)
N’-phenylcyclohexane
5.56.0
6.76.87.1
15
phenylcyclohexane-1,2-diamine (3s)
4.04.55.0f1 (ppm)
6.56.6
diamine (3s)
3.03.54.0 2.02.5
1.01.5
0.00.5
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-(1-Naphthyl)--N'-phenylcyclohexane
phenylcyclohexane-1,2-diamine (
16
diamine (3t)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-(2,4-Diflurophenyl)Diflurophenyl)-N’-phenylcyclohexanephenylcyclohexane
17
phenylcyclohexane-1,2-diamine (3u)
diamine (3u)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-(3,4-Dimethoxyphenyl)Dimethoxyphenyl)-N’-phenylcyclohexane
phenylcyclohexane
18
phenylcyclohexane-1,2-diamine (3v)diamine (3v)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
N-Phenyl-N’-(3,4,5(3,4,5-trimethoxyphenyl)cyclohexane
trimethoxyphenyl)cyclohexane
19
trimethoxyphenyl)cyclohexane-1,2-diamine (3w)
diamine (3w)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,1’S,2S
S,2’S)-N1,N1’-(1,4(1,4-Phenylene)bis(Phenylene)bis(N2-phenylcyclohexane
20
phenylcyclohexane-1,2
1,2-diamine) (3x)diamine) (3x)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
4-((1S,2S)
)-2-(Phenylamino)cyclopentylamino)benzenethiol (Phenylamino)cyclopentylamino)benzenethiol (
Phenylamino)cyclopentylamino)benzenethiol (
21
Phenylamino)cyclopentylamino)benzenethiol (4e)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
(1S,2S)-N
(2S,3S)-N
9.09.5
N-(2-Methoxyphenyl)
N2,N3-Diphenyl-
8.08.59.0
Methoxyphenyl)-N’-phenylcyclopentan
-1,2,3,4-tetrahydronaphthalen
7.07.58.0
phenylcyclopentan
tetrahydronaphthalen
6.06.5
22
phenylcyclopentan-1,2-diamine (4f)
tetrahydronaphthalen-2,3-diamine (6a)
5.05.5f1 (ppm)
(4f)
diamine (6a)
4.04.5 3.03.5 1.52.02.5
1.5
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
4-[(2S,3S)
[(2S,3S)-3-(phenylamino)butan(phenylamino)butan-2-ylamino]ylamino]benzenethiol (7b
23
benzenethiol (7b)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
24
(1R,3S,4S,6S)-N,N’-Diphenyl-7-tosyl-7-azabicyclo[4.1.0]-heptane-3,4-diamine (8a)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
25
(3S,4S)-N,N’-Diphenyltetrahydrofuran-3,4-diamine (9a)
(5S,6S)-2,2-Dimethyl-N,N’-diphenyl-1,3-dioxepan-5,6-diamine (10a)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.66.76.86.97.27.3f1 (ppm)
3.73.83.94.04.14.24.3f1 (ppm)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.706.757.207.25f1 (ppm)
3.453.503.553.60f1 (ppm)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
26
(5S,6S)-Methyl-4-((-2,2-dimethyl-6-(phenylamino)-1,3-dioxepan-5-yl)amino)benzoate (10b)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.76.87.27.37.87.9f1 (ppm)
4.04.1f1 (ppm)
3.53.6f1 (ppm)
0102030405060708090100110120130140150160170f1 (ppm)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
27
(5S,6S)-4-(2,2-Dimethyl-6-(phenylamino)-1,3-dioxepan-5-yl)aS. 27mino)benzonitrile (10c)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.43.53.63.73.83.94.04.1f1 (ppm)
6.76.87.27.37.47.5f1 (ppm)
0102030405060708090100110120130140150f1 (ppm)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013