In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ...
Transcript of In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ...
![Page 1: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/1.jpg)
1
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
![Page 2: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/2.jpg)
2
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 3: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/3.jpg)
3
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 4: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/4.jpg)
4
Figure S1: 1H-NMR spectrum of (R/S)-4-fluoro-α-methylbenzylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 5: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/5.jpg)
5
Figure S2: 1H-NMR spectrum of (R/S)-4-methoxy-α-Methylbenzylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 6: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/6.jpg)
6
Figure S3: 1H-NMR spectrum of (R/S)-4-methyl-α-Methylbenzylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 7: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/7.jpg)
7
Figure S4: 1H-NMR spectrum of (R/S)-sec-butylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 8: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/8.jpg)
8
Figure S5: 1H-NMR spectrum of (R/S)-α-ethylbenzylamine.
Figure S6: 1H-NMR spectrum of (R/S)-α-methylnapthylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 9: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/9.jpg)
9
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 10: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/10.jpg)
10
Figure S7: 1H-NMR spectrum of (R/S)-α-methylbenzylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 11: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/11.jpg)
11
Figure S8: 1H-NMR spectrum of (R/S)-1,2-diphenylethyalamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 12: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/12.jpg)
12
Figure S9: 1H-NMR spectrum of (R/S)-1-aminoindane.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 13: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/13.jpg)
13
Figure S10: 1H-NMR spectrum of (R/S)-1-cyclohexylethylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 14: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/14.jpg)
14
Figure S11: 1H-NMR spectrum of (R/S)-2-methylpiperidine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 15: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/15.jpg)
15
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.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 16: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/16.jpg)
16
Figure S13: 1H-NMR spectrum of (R/S)-2-methylpiperazine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 17: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/17.jpg)
17
Figure S14: 1H-NMR spectrum of (R/S)-ethylpiperidine-3-carboxylate.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 18: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/18.jpg)
18
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.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 19: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/19.jpg)
19
Figure S16: 1H-NMR spectrum of (R/S)-N,N-dimethylphenylethylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 20: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/20.jpg)
20
Figure S17: 1H-NMR spectrum of (R/S)-2,amino,1,2-diphenylethanol.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 21: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/21.jpg)
21
Figure S18: 1H-NMR spectrum of (R/S)-2-Phenylglycinol.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 22: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/22.jpg)
22
Figure S19: 1H-NMR spectrum of (R/S)-1-Amino, 2-indanol.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 23: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/23.jpg)
23
Figure S20: 1H-NMR spectrum of (R/S)-2-amino-1-butanol.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 24: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/24.jpg)
24
Figure S21: 1H-NMR spectrum of (R/S)-α-α-diphenyl-2-pyrrolidinemethanol.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 25: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/25.jpg)
25
Figure S22: 1H-NMR spectrum of (R/S)-2-piperidinemethanol.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 26: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/26.jpg)
26
Figure S23: 1H-NMR spectrum of (R/S)-2-fluorobenzylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 27: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/27.jpg)
27
Figure S24: 1H-NMR spectrum of (R/S)-benzylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 28: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/28.jpg)
28
Figure S25: 1H-NMR spectrum of (R/S)-isopropylamine.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 29: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/29.jpg)
29
Figure S26: 1H-NMR spectrum of (R/S)-2-amino-2-methyl-1-propanol.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 30: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/30.jpg)
30
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
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013
![Page 31: In situ Approach for Testing the Enantiopurity of Chiral ... · 1 Supporting Information In situ Approach for Testing the Enantiopurity of Chiral Amines and Amino Alcohols by 1H NMR](https://reader034.fdocuments.us/reader034/viewer/2022042300/5eca749330e8122e385e3030/html5/thumbnails/31.jpg)
31
.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013