the ti-binolate-catalyzed, enantioselective ring-opening ... file1 the ti-binolate-catalyzed,...

1

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


[6 BINOL + 3 Ti + H]+ C120H73O12Ti3 1849.35350 1849.36931 8

Table 3 Results after addition of 10 eq. aziridine 1a in CH2Cl2


[6 BINOL + 4 Ti + 4 H2O + 3 aziridine +

3 aniline]+

C174H143N6O16Ti4 2764.84730 2764.81534 11


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


[2 11 + 2 Ti + H2O - H]- C84H3O11Ti2 1333.25523 1333.25118 3

Table 5 Additional Species with CH2Cl2/MeCN as solvent


[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


[2 11 + 2 Ti + aziridine + aniline + H]+ C102H75N2O10Ti2 1583.4381 1583.43296 3


Experimental Data of new compounds/Compounds synthesized by a new method

(1S,2S)-N


N-(4-Chlorophenyl)


Chlorophenyl)-N’-phenylcyclohexane


phenylcyclohexane-1,2

4


1,2-diamine (3e)


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


(1S,2S)-N

N-(Phenyl)-N’-(4(4-trifluoromethylphenyl)

trifluoromethylphenyl)-cyclohexane

5

cyclohexane-1,2--diamine (3g)


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


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(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)


4-((1S,2S)

)-2-(Phenylamino)(Phenylamino)cyclohexylamino)cyclohexylamino)benzenethiol (3k

8

benzenethiol (3k)


(1S,2S)-N

N-Phenyl-N’-m--tolylcyclohexane

tolylcyclohexane-1,2-diamine (3l)

9

diamine (3l)


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)


(1S,2S)-N

N-(3-Bromophenyl)Bromophenyl)-N’-phenylcyclohexane


11

1,2-diamine (3n)diamine (3n)


(1S,2S)-N

N-Phenyl-N’-(3--trifluoromethylphenyl)cyclohexane

trifluoromethylphenyl)cyclohexane

12

trifluoromethylphenyl)cyclohexane-1,2-diamine (3o)diamine (3o)


(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


(1S,2S)-N

N-(2-Flurophenyl)Flurophenyl)-N’-phenylcyclohexanephenylcyclohexane-1,2

14

,2-diamine (3r)(3r)


(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


(1S,2S)-N

N-(1-Naphthyl)--N'-phenylcyclohexane

phenylcyclohexane-1,2-diamine (

16

diamine (3t)


(1S,2S)-N

N-(2,4-Diflurophenyl)Diflurophenyl)-N’-phenylcyclohexanephenylcyclohexane

17

phenylcyclohexane-1,2-diamine (3u)

diamine (3u)


(1S,2S)-N

N-(3,4-Dimethoxyphenyl)Dimethoxyphenyl)-N’-phenylcyclohexane

phenylcyclohexane

18

phenylcyclohexane-1,2-diamine (3v)diamine (3v)


(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)


(1S,1’S,2S

S,2’S)-N1,N1’-(1,4(1,4-Phenylene)bis(Phenylene)bis(N2-phenylcyclohexane

20


1,2-diamine) (3x)diamine) (3x)


4-((1S,2S)

)-2-(Phenylamino)cyclopentylamino)benzenethiol (Phenylamino)cyclopentylamino)benzenethiol (

Phenylamino)cyclopentylamino)benzenethiol (

21

Phenylamino)cyclopentylamino)benzenethiol (4e)


(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


4-[(2S,3S)

[(2S,3S)-3-(phenylamino)butan(phenylamino)butan-2-ylamino]ylamino]benzenethiol (7b

23

benzenethiol (7b)


24

(1R,3S,4S,6S)-N,N’-Diphenyl-7-tosyl-7-azabicyclo[4.1.0]-heptane-3,4-diamine (8a)


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)


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)


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)


the ti-binolate-catalyzed, enantioselective ring-opening ... file1 the ti-binolate-catalyzed,...

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