in situ approach for testing the enantiopurity of chiral ... · 1 supporting information in situ...

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Supporting Information

In situ Approach for Testing the Enantiopurity of Chiral Amines and

Amino Alcohols by 1H NMR

Sandeep Kumar Mishra, Sachin R. Chaudhari, and N. Suryaprakash*

NMR Research Centre, Solid State and Structural Chemistry Unit,

Indian Institute of Science, Bangalore-560012

*Corresponding Author

e-mail: [email protected]

Tel: 0091 80 22933300, 919845124802

Fax: 0091 8023601550

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013

mailto:[email protected]

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Table of contents pages

NMR spectra

S1: 1H-NMR spectrum of (R/S)-4-fluoro-α-methylbenzylamine…………………………..4

S2: 1H-NMR spectrum of (R/S)-4-methoxy-α-Methylbenzylamine. ……………………..5

S3: 1H-NMR spectrum of (R/S)-4-methyl-α-Methylbenzylamine. ……………………….6

S4: 1H-NMR spectrum of (R/S)-sec-butylamine. …………………………………………7

S5: 1H-NMR spectrum of (R/S)-α-ethylbenzylamine. ……………………………………8

S6: 1H-NMR spectrum of (R/S)-α-methylnapthylamine. …………………………………9

S7: 1H-NMR spectrum of (R/S)-α-methylbenzylamine. …………………………………10

S8: 1H-NMR spectrum of (R/S)-1,2-diphenylethyalamine. ….……...……………………11

S9: 1H-NMR spectrum of (R/S)-1-aminoindane. ..……………...………………………...12

S10: 1H-NMR spectrum of (R/S)-1-cyclohexylethylamine. …………………………….13

S11: 1H-NMR spectrum of (R/S)-2-methylpiperidine. …………………………………..14

S12: 1H-NMR spectrum of (R/S)-N-α-dimethylbenzylamine. ……………..……………15

S13: 1H-NMR spectrum of (R/S)-2-methylpiperazine. …………………………………16

S14: 1H-NMR spectrum of (R/S)-ethylpiperidine-3-carboxylate. ………………………17

S15: 1H-NMR spectrum of (R/S)-N-methyl-1-(-naphthyl)ethylamine. ………………….18

S16: 1H-NMR spectrum of (R/S)-N,N-dimethylphenylethylamine. …………………….19

S17: 1H-NMR spectrum of (R/S)-2,amino,1,2-diphenylethanol. ………………………20

S18: 1H-NMR spectrum of (R/S)-2-Phenylglycinol. …………………………………….21

S19: 1H-NMR spectrum of (R/S)-1-Amino, 2-indanol. …………………………………..22

S20: 1H-NMR spectrum of (R/S)-2-amino-1-butanol. …………………………………...23


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S21: 1H-NMR spectrum of (R/S)-α-α-diphenyl-2-pyrrolidinemethanol. ………………….24

S22: 1H-NMR spectrum of (R/S)-2-piperidinemethanol. ………………………………...25

S23: 1H-NMR spectrum of (R/S)-2-fluorobenzylamine. …………………………………26

S24: 1H-NMR spectrum of (R/S)-benzylamine. …………………………………………..27

S25: 1H-NMR spectrum of (R/S)-isopropylamine. ………………………………………..28

S26: 1H-NMR spectrum of (R/S)-2-amino-2-methyl-1-propanol. …………………………29

S27: (a): 11B NMR spectrum of Triphenyl borate (without complexation)…………..……30

(b): boron complexed with R-BINOL and chiral amine………………………………31


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Figure S1: 1H-NMR spectrum of (R/S)-4-fluoro-α-methylbenzylamine.


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Figure S2: 1H-NMR spectrum of (R/S)-4-methoxy-α-Methylbenzylamine.


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Figure S3: 1H-NMR spectrum of (R/S)-4-methyl-α-Methylbenzylamine.


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Figure S4: 1H-NMR spectrum of (R/S)-sec-butylamine.


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Figure S5: 1H-NMR spectrum of (R/S)-α-ethylbenzylamine.

Figure S6: 1H-NMR spectrum of (R/S)-α-methylnapthylamine.


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Figure S7: 1H-NMR spectrum of (R/S)-α-methylbenzylamine.


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Figure S8: 1H-NMR spectrum of (R/S)-1,2-diphenylethyalamine.


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Figure S9: 1H-NMR spectrum of (R/S)-1-aminoindane.


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Figure S10: 1H-NMR spectrum of (R/S)-1-cyclohexylethylamine.


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Figure S11: 1H-NMR spectrum of (R/S)-2-methylpiperidine.


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Figure S12: 1H-NMR spectrum of (R/S)-N-α-dimethylbenzylamine.

Please note: The differential intensity for CH3 group is arising because of the formation of

salt by one enantiomer. This causes the broadening of the signal. However, the equal

integrated intensity confirms, there is no kinetic resolution.


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Figure S13: 1H-NMR spectrum of (R/S)-2-methylpiperazine.


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Figure S14: 1H-NMR spectrum of (R/S)-ethylpiperidine-3-carboxylate.


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Figure S15: 1H-NMR spectrum of (R/S)-N-methyl-1-(-naphthyl)ethylamine.

Please note: The differential intensity for CH3 group (proton a) is arising because of the

formation of salt by one enantiomer. This is confirmed by using enantiopure compound.

This causes the broadening of the signal. However, the equal integrated intensity confirms,

there is no kinetic resolution.


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Figure S16: 1H-NMR spectrum of (R/S)-N,N-dimethylphenylethylamine.


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Figure S17: 1H-NMR spectrum of (R/S)-2,amino,1,2-diphenylethanol.


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Figure S18: 1H-NMR spectrum of (R/S)-2-Phenylglycinol.


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Figure S19: 1H-NMR spectrum of (R/S)-1-Amino, 2-indanol.


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Figure S20: 1H-NMR spectrum of (R/S)-2-amino-1-butanol.


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Figure S21: 1H-NMR spectrum of (R/S)-α-α-diphenyl-2-pyrrolidinemethanol.


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Figure S22: 1H-NMR spectrum of (R/S)-2-piperidinemethanol.


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Figure S23: 1H-NMR spectrum of (R/S)-2-fluorobenzylamine.


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Figure S24: 1H-NMR spectrum of (R/S)-benzylamine.


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Figure S25: 1H-NMR spectrum of (R/S)-isopropylamine.


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Figure S26: 1H-NMR spectrum of (R/S)-2-amino-2-methyl-1-propanol.


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Figure S27: Comparison of 11

B NMR spectrum of top trace: Triphenyl borate (without

complexation) bottom trace: boron complexed with R-BINOL and chiral amine at the

optimum condition of amine. Peak around at 8 ppm indicating the formation of a tetragonal

boronate species. And it is more intense at the optimum condition


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in situ approach for testing the enantiopurity of chiral ... · 1 supporting information in situ...

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