supporting information ester derivatives. derived imines ... · 6500 me b o o ome o 3gii. 8.0 7.5...
TRANSCRIPT
![Page 1: Supporting Information ester derivatives. derived imines ... · 6500 Me B O O OMe O 3gii. 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 f1 (ppm)-2000-1000](https://reader033.vdocuments.net/reader033/viewer/2022060721/608177afbb31eb7dcc32d4c2/html5/thumbnails/1.jpg)
Supporting Information
One-pot catalytic asymmetric borylation of unsaturated aldehyde-
derived imines; functionalisation to homoallylic boronate carboxylate
ester derivatives.
Alba Pujol, Adam D. J. Calow, Andrei S. Batsanov and Andrew Whiting
1. ReactIR studies on in situ imine formation
2. Chiral HPLC
3. 1H, 13C, 11B NMR spectra
4. Crystallographic structures and data
5. References
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2015
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1. ReactIR studies on in situ imine formation
R
O
1
H2NPh
Ph(1.0 equiv)
3Å-MS, iPrOH, r.t.R
N
4
Ph
Ph
Scheme 1 Formation of α,β-unsaturated imines in iPrOH.
Standard conditions: To an oven-dried two-necked flask, fitted with the IR probe, enal (2.0
mmol) was added to a stirring solution of solvent (8.0 mL) and 3 Å-molecular sieve beads
(2.0 g, oven-dried at 250 ºC for >48 h prior to use), under argon at 25 ºC. Once the C=O peak
had plateaued (observed through PC-interface), showing maximum intensity, amine (2.0
mmol) was added and the reaction was carried out for 0.5 – 24 h. The in situ-formed imine
was then utilised without purification by using a needle-syringe combination.
Representative graphical output of the reaction between Cinnamaldehyde 1a and benzhydryl
amine (see standard conditions).
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Reaction profile of 2-Hexenal 1d and benzhydryl amine (see standard conditions).
Reaction profile of Crotonaldehyde 1g and benzhydryl amine (see standard conditions).
Reaction profile of (2E)-3-(Thiophen-2-yl)prop-2-enal 1j and benzhydryl amine (see standard
conditions).
![Page 4: Supporting Information ester derivatives. derived imines ... · 6500 Me B O O OMe O 3gii. 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 f1 (ppm)-2000-1000](https://reader033.vdocuments.net/reader033/viewer/2022060721/608177afbb31eb7dcc32d4c2/html5/thumbnails/4.jpg)
2. Chiral HPLC
Sample chromatograms: 1) Racemic standard; 2) Optimised asymmetric reaction (IPA, (R)-
DM BINAP as ligand, unless otherwise stated).
BOO
OMe
O
3aii
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MeO
B
OMe
OOO
3bii
Optimised asymmetric reaction (THF/MeOH, (R)-DM-BINAP as ligand)
![Page 6: Supporting Information ester derivatives. derived imines ... · 6500 Me B O O OMe O 3gii. 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 f1 (ppm)-2000-1000](https://reader033.vdocuments.net/reader033/viewer/2022060721/608177afbb31eb7dcc32d4c2/html5/thumbnails/6.jpg)
BOO
OMe
O
3dii
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Cl
B
OMe
OOO
3eii
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Optimised asymmetric reaction (THF/MeOH, (R)-DM-BINAP as ligand)
BOO
OMe
O
3fii
![Page 9: Supporting Information ester derivatives. derived imines ... · 6500 Me B O O OMe O 3gii. 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 f1 (ppm)-2000-1000](https://reader033.vdocuments.net/reader033/viewer/2022060721/608177afbb31eb7dcc32d4c2/html5/thumbnails/9.jpg)
BOO
OMe
O
3gii
![Page 10: Supporting Information ester derivatives. derived imines ... · 6500 Me B O O OMe O 3gii. 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 f1 (ppm)-2000-1000](https://reader033.vdocuments.net/reader033/viewer/2022060721/608177afbb31eb7dcc32d4c2/html5/thumbnails/10.jpg)
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OMe
BO O
O
3iii
Stereochemical assignments
The relative stereochemistry of each chiral compound can be determined through the use of
chiral HPLC (see above). In addition, the absolute stereochemistry of each product is
assumed to be consistent with previous studies in our group,1 whereby derivatisation and
X-ray analysis allowed for the absolute stereochemistry of the respective compounds to be
assigned. This was later supported by derivatisation of such compounds into known
pharmaceuticals,2 whereby the absolute stereochemistry was consistent with those
independently verified by this work.1
3. 1H, 13C and 11B NMR spectra
It is important to note that samples 6a-c, 7b and 7d could not be purified due to their inherent
instability. Therefore, the crude 1H-NMR spectra of 6a-c, 7b and 7d are listed below.
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
Crude 1H-NMR showing the presence of 6a
Ph O
BOO
6a
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
0
200
400
600
800
1000
1200
1400
1600
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2000
2200
2400
2600
2800
p-OMePh O
BOO
6b
Crude 1H-NMR showing the presence of 6b 4a
![Page 14: Supporting Information ester derivatives. derived imines ... · 6500 Me B O O OMe O 3gii. 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 f1 (ppm)-2000-1000](https://reader033.vdocuments.net/reader033/viewer/2022060721/608177afbb31eb7dcc32d4c2/html5/thumbnails/14.jpg)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-50
0
50
100
150
200
250
300
350
400
450
500
550
600
650
O
BOO
6c
Crude 1H-NMR showing the presence of 6c 4a
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
p-OMePh
BOO
7bO
OCrude 1H-NMR showing the presence of 7b 4a
![Page 16: Supporting Information ester derivatives. derived imines ... · 6500 Me B O O OMe O 3gii. 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 f1 (ppm)-2000-1000](https://reader033.vdocuments.net/reader033/viewer/2022060721/608177afbb31eb7dcc32d4c2/html5/thumbnails/16.jpg)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-200
0
200
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600
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1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
3800
Pr
BOO
7dO
O
Crude 1H-NMR showing the presence of 7d 4a
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-1000
0
1000
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6000
7000
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Ph
BOO
OEt
O
3ai
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-100102030405060708090100110120130140150160170180190200210f1 (ppm)
-200
0
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Ph
BOO
OEt
O
3ai
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-25-20-15-10-5051015202530354045505560f1 (ppm)
-1500
-1000
-500
0
500
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Ph
BOO
OEt
O
3ai
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
Ph
BOO
OMe
O
3aii
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0102030405060708090100110120130140150160170f1 (ppm)
-500
0
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Ph
BOO
OMe
O
3aii
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510152025303540455055606570f1 (ppm)
-1000
-500
0
500
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Ph
BOO
OMe
O
3aii
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
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p-OMePh
BOO
OMe
O
3bii
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0102030405060708090100110120130140150160170f1 (ppm)
-200
0
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600
800
1000
1200
1400
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p-OMePh
BOO
OMe
O
3bii
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46810121416182022242628303234363840424446485052545658606264f1 (ppm)
-500
0
500
1000
1500
2000
p-OMePh
BOO
OMe
O
3bii
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0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
-1000
0
1000
2000
3000
4000
5000
6000
7000
8000
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10000
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Pr
BOO
OMe
O
3dii
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0102030405060708090100110120130140150160170f1 (ppm)
-500
0
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Pr
BOO
OMe
O
3dii
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-25-20-15-10-50510152025303540455055606570f1 (ppm)
-500
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Pr
BOO
OMe
O
3dii
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
-20
0
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p-ClPh
BOO
OMe
O
3eii
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0102030405060708090100110120130140150160170f1 (ppm)
-100
0
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p-ClPh
BOO
OMe
O
3eii
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68101214161820222426283032343638404244464850525456f1 (ppm)
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p-ClPh
BOO
OMe
O
3eii
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0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
0
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Et
BOO
OMe
O
3fii
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0102030405060708090100110120130140150160170f1 (ppm)
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Et
BOO
OMe
O
3fii
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-5051015202530354045505560f1 (ppm)
-500
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Et
BOO
OMe
O
3fii
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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
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0102030405060708090100110120130140150160170f1 (ppm)
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051015202530354045505560f1 (ppm)
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-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
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-505101520253035404550556065f1 (ppm)
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4. Crystallographic data
Figure X1. X-ray molecular structure of compound 4a at 120 K. Here and below, atomic
displacement ellipsoids are drawn at 50% probability level.
Figure X2. X-ray molecular structure of compound 4b at 120 K.
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Figure X3. X-ray molecular structure of compound 4e at 120 K.
Figure X4. Two independent molecules in the crystal structure of compound 4h at 120 K.
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Figure X5. X-ray molecular structure of compound 4j at 120 K; the thiophene ring is disordered
between two opposite orientations in 4:1 ratio (minor atom positions are primed).
5. References
1. A. D. J. Calow, A. Batsanov, A. Pujol, C. Solé, E. Fernández, A. Whiting, Org. Lett., 2013, 15, 4810-4813
2. A. D. J. Calow, E. Fernández, A. Whiting, Org. Biomol. Chem., 2014, 12, 6121-6127.