pentaerythritol – imine macrocycles ...1 supplementaryintroduction materialof axial for chirality...
TRANSCRIPT
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Supplementary Material for
Introduction of Axial Chirality at a Spiro Carbon Atom in Synthesis of a Pentaerythritol – Imine MacrocyclesJ. Grajewski,a K. Piotrowska,a M. Zgorzelak,a U. Rychlewska,a A. Janiak,a K. Biniek-Antosiaka, and J. Gawronskia
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018
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Table of Contents
Figure S1. Eight unique conformational permutations of the structure of A, including enantiomers..........3
Figure S2. An illustration of asymmetric unit of 9 together with labelling scheme. .....................................4
Figure S3. An overlay of the molecules of 9 obtained from the crystal structure (blue) and the gas phase calculations (magenta). .................................................................................................................................5
Figure S4. Top (a) and side (b) space-fill view of molecular arrangement in the crystals of 9. .....................6
Table S1. Comparison of selected torsion angles describing molecular conformation of 9 as present in crystals with the one calculated at the B3LYP/6-311g(d,p) level in the gas phase. ......................................7
Table S2. C-H…O intermolecular interactions in the crystals of 9. ................................................................8
Table S3. Crystal data, structure refinement parameters for compound 9. .................................................9
Spectra of 3 .................................................................................................................................................10
Spectra of 5 .................................................................................................................................................12
HRMS Spectrum of 7 ...................................................................................................................................16
Spectra of 8 .................................................................................................................................................18
Spectra of 9 .................................................................................................................................................20
Figure S5. Experimental CD spectra of 9. (solid line), calculated (dashed line) and calculated for a diastereoisomer of 9 (dotted line) with opposite (P) helicity of both spiro fragments (not found in reaction). .....................................................................................................................................................25
Figure S6. Calculated structure of diastereoisomer of 9 with opposite (P) helicity (not found in reaction). .....................................................................................................................................................26
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Figure S1. Eight unique conformational permutations of the structure of 1, including enantiomers.
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Crystal structure
Figure S2. An illustration of asymmetric unit of 9 together with labelling scheme. Ellipsoids are drawn at the 40% probability level, hydrogen atoms are represented by spheres of arbitrary radii.
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Figure S3. An overlay of the molecules of 9 obtained from the crystal structure (blue) and the gas phase calculations (magenta).
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Packing in crystals of 9
The rotational behavior of spiroacetal rhombimine 9 in crystal largely depends on the strong intermolecular C-H∙∙∙O hydrogen bonding interactions. The interactions cause partial interpenetration of the neighbouring molecules, as illustrated in Fig. S4. The angle between two interpenetrating rings amounts to 76.5°. Geometrical parameters describing these interactions are listed in Table S2.
Figure S4. Top (a) and side (b) space-fill view of molecular arrangement in the crystals of 9. Each macrocycle uses the spiro unit to partially penetrate the cavity of its neighbour. c) C-H...O interactions between two adjacent molecules.
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Table S1. Comparison of selected torsion angles describing molecular conformation of 9 as present in crystals with the one calculated at the B3LYP/6-311g(d,p) level in the gas phase.
X-ray Calculated
N1-C1-C2-N2 -70.8(3) -63.9
C1-C2-N2-C7 106.5(3) 125.9
N2-C7-C8-C9 3.3(5) 179.9
C7-C8-C9-C10 174.9(3) -175.7
C8-C9-C10-C11 1.0(6) 0.7
C9-C10-C11-C14 -175.7(3) 180
C10-C11-C14-O1 -165.4(3) -7.2
C11-C14-O1-C15 176.5(3) 178.8
C14-O2-C15-C17 -56.8(4) 57.8
O2-C15-C17-C18 -171.7(3) -173.6
C15-C17-C18-O3 -172.7(3) -172.1
C17-C18-O3-C20 59.3(4) 57.2
C18-O3-C20-C21 175.8(3) 179.4
O3-C20-C21-C22 14.5(4) -137.4
C20-C21-C22-C23 -179.0(3) -177.1
C21-C22-C23-C24 -0.4(5) 0.2
C22-C23-C24-C27 179.2(3) 179.0
C23-C24-C27-N3 -169.4(3) 2.6
C24-C27-N3-C28 179.7(3) -179.7
C27-N3-C28-C29 127.5(3) 121.9
N3-C28-C29-N4 -62.2(4) -63.9
C28-C29-N4-C34 103.3(4) 125.9
C29-N4-C34-C35 177.0(3) 179.9
N4-C34-C35-C36 -4.4(5) 4.9
C34-C35-C36-C37 179.0(3) 179.1
C35-C36-C37-C38 1.3(5) 0.5
C36-C37-C38-C41 -175.4(3) 179.4
C37-C38-C41-O5 -138.8(3) 173.4
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C38-C41-O5-C42 -173.4(2) 178.8
C41-O5-C42-C44 57.9(3) 57.8
O5-C42-C44-C45 -177.1(2) -173.6
C42-C44-C45-O7 -174.4(2) -172.1
C44-C45-O7-C47 57.3(3) 57.2
C45-O7-C47-C48 -177.1(2) 179.4
O7-C47-C48-C49 -96.5(3) 45.0
C47-C48-C49-C50 169.8(3) 176.9
C48-C49-C50-C51 -1.3(5) 0.2
C49-C50-C51-C54 -172.4(3) -179.1
C50-C51-C54-N1 -3.3(5) -177.9
C51-C54-N1-C1 176.2(3) -179.7
C54-N1-C1-C2 98.7(3) 122.0
Table S2. C-H…O intermolecular interactions in the crystals of 9.C-H (Å) H…O (Å) C…O (Å) C-H…O (°) Symm
C14-H14…O4 1.00 2.64 3.638(4) 172 x-1/2, -y+3/2, -z+1
C42-H42B…O6 0.99 2.22 3.193(4) 166 x+1/2, -y+1/2, -z+1
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Table S3. Crystal data, structure refinement parameters for compound 9.9
Chemical formula C54H60N4O8Mr 893.06
Crystal system, space group
Orthorhombic, P212121
Temperature (K) 150
a, b, c (Å) 10.7257 (2), 11.3249 (2), 39.4835 (5)
V (Å3) 4795.96 (14)
Z 4
Radiation type Cu Kα
Μ (mm-1) 0.67
Crystal size (mm) 0.30 × 0.20 × 0.12
Diffractometer SuperNova
Absorption correction
Multi-scan
Tmin, Tmax 0.846, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections
20339, 9822, 9564
Rint 0.026
(sin θ/λ)max (Å-1) 0.631
R[F2 > 2σ(F2)], wR(F2), S
0.049, 0.134, 1.07
No. of reflections 9822
No. of parameters 595
H-atom treatment H-atom parameters constrained
max, min (e Å-3) 0.56, -0.25
Absolute structure parameter
0.24 (10)
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1H and 13C NMR spectra were recorded on a Bruker 400 MHz or Varian Mercury 300 MHz at ambient temperature. All 1H NMR spectra are reported in parts per million (ppm) downfield of TMS and were measured relative to the signals for CDCl3 (7.27 ppm). All 13C NMR spectra were reported in ppm relative to residual CDCl3 (77.0 ppm) and were obtained with 1H decoupling. MS spectra were recorded on impact HD Bruker apparatus.
Spectra of 3
OB
O
O
OBO
O
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
8.00
4.13
4.05
2.00
-0.0
0
1.56
4.11
7.26
7.85
7.86
7.86
7.87
7.88
7.88
7.95
7.95
7.96
7.97
10.0
6
1H NMR (400 MHz, CDCl3 + TMS)
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0102030405060708090100110120130140150160170180190f1 (ppm)
-2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
30000
32000
34000
36000
38000-0.0
01.
02
29.7
0
36.6
6
64.9
3
76.6
877
.00
77.3
2
115.
87
128.
71
134.
44
138.
06
192.
71
13C NMR (100 MHz, CDCl3+ TMS):
MS spectra – ionization EI, positive mode
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Spectra of 5
N
N N
NBO
O
OB
O
BO
O
OB
O
1H NMR (400 MHz, CDCl3):
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13C NMR (100 MHz,CDCl3):
MS spectra – ionization EI, positive mode
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HSQC spectrum of 5 (upper panel) and zoom (lower panel)
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NOESY spectrum of 5 (upper panel) and zoom (lower panel)
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HRMS Spectrum of 7
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1H NMR of 7
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Spectra of 8
O
O
O
O
O
O
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0(ppm)
2.0
4.0
2.0
2.0
4.0
4.0
2.0
0.00
3.68
3.72
3.85
3.86
3.89
3.90
4.83
4.84
4.87
4.88
5.53
7.26
7.65
7.68
7.89
7.89
7.90
7.91
7.92
7.92
10.0
3
1H NMR (300 MHz, CDCl3)
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0102030405060708090100110120130140150160170180190200(ppm)
0.00
32.6
3
70.5
170
.99
76.6
177
.04
77.2
377
.45
101.
22
126.
8112
9.73
136.
78
143.
78
191.
94
13C NMR (75 MHz, CDCl3)
MS spectra – ionization EI, positive mode
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Spectra of 9
N
N N
NO
O
O
O
O
O
O
O
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5(ppm)
4.0
4.0
8.0
4.0
4.0
8.0
8.0
4.0
-0.0
0
1.49
1.59
1.88
3.34
3.37
3.58
3.61
3.76
3.78
3.78
3.79
3.80
4.74
4.76
5.40
7.26
7.39
7.41
7.52
7.54
8.14
1H NMR (400 MHz, CDCl3)
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0102030405060708090100110120130140150160(ppm)
0.00
24.4
9
32.5
132
.70
70.4
670
.88
73.7
076
.70
77.0
277
.22
77.3
4
101.
89
126.
3812
7.80
136.
83
139.
77
161.
04
13C NMR (100 MHz, CDCl3)
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HSQC spectrum of 9 (CDCl3)
Expansion of HSQC spectrum of 9 (CDCl3)
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COSY spectrum of 9 (CDCl3)
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HRMS spectra of 9 – ionization ESI, positive mode
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Figure S5. Experimental CD spectra of 9. (solid line), calculated (dashed line) and calculated for a diastereoisomer of 9 (dotted line) with opposite (P) helicity of both spiro fragments (not found in reaction). Main pattern of Cotton effects remains the same due to similar arrangement of phenyl and imine groups, slight red shift and increase of magnitude can be observed.
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Figure S6. Calculated structure of diastereoisomer of 9 with opposite (P) helicity (not found in reaction).