Supplementary Information:
Theoretical and Experimental Studies of 1,3-Dipolar Cycloaddition
Reactions Between Trimethylsilylazide and Citral (Geranial & Neral)
Sepehr Taban1, Avat (Arman) Taherpour*2,3
1
Chemistry Department, Science Faculty, Islamic Azad University, Arak Branch, P. O. Box 38135-567, Arak, Iran
2
Department of Organic Chemistry, Faculty of Chemistry, Razi University, P.O.Box: 67149-67346,
Kermanshah, Iran
3
Medical Biology Research Center, Kermanshah University of Medical Sciences, Kermanshah, Iran
Table of contents:
S1: The bond lengths (Å) and bond angles (°) of Geranial (1), Neral (2) and trimethylsilylazide
(TMS).
S2: The Mulliken charges of Geranial (1), Neral (2) and trimethylsilyl azide. The Mulliken charges
are important to the pathway regio-selective determination.
S3: The selected structural data for the intermediates, the carbenes 11 & 12 and biradicals 13 & 14.
S4: The resonance forms of 3-amino-3-diazo-3,7-dimethyloct-6-enal (7).
S5: The transition states ([TS]9 and [TS]10) of the N2 elimination from (6) and (8).
S6: The bi-radical intermediates (13) and (14) to produce aziridine (15) (3R,4S) and (3S, 4S).
S7: The structure of the singlet carbene intermediate (11).
S8: The transition states ([TS]15 and [TS]15’) of the aziridines (15) formation.
S9: The products of aziridine (15) (3R,4S) and (3S, 4S).
S10: The diagram of the GC spectrum related to the GC-MS experimental part of this study.
S11: The mass spectrum of the aziridine derivative 15 (A, B and C) related to the experimental
part of this study. The retention times (RT) in GC-Mass experiment was 4.43, 8.29 and
9.20min under the spectroscopy conditions.
S1: The bond lengths (Å) and bond angles (°) of Geranial (1), Neral (2) and trimethylsilylazide
(TMS). The structures were calculated by theory (DFT) B3LYP/6-31G* method.
S2: The Mulliken charges of Geranial (1), Neral (2) and trimethylsilyl azide. The Mulliken charges
are important to the pathway regio-selective determination. The structures were calculated by
theory (DFT) B3LYP/6-31G* method.
S3: The selected structural data for the intermediates, the carbenes 11 & 12 and biradicals 13 &
14. The intermediate structures were calculated by theory (DFT) B3LYP/6-31G* method.
Selected data
Bond length(Å)
N1N2
N2N3
N1C4
N3C3
C3C4
N1X7 a
C4C5
C4C6
C2C3
O1C2
C2H8
C3H9
Bond angle(°)
N1N2N3
N2N3C3
N3C3C4
C3C4N1
C4N1N2
N2N1X7 a
C4N1X7 a
C2C3H8
C4N1C3
N1C3C4
N1N2N3
Torsional angle(°)
C4N1N2N3
N1N2N3C3
N2N3C3C4
N3N2N1X7
C3C4N1X7
C2C3C4C6
O1C2C3H9
C5C4C3H9
a
Carbenes
[In.]11 (s)
[In.]12 (t)
Biradicals
[In.]13
[In.]14
1.521
1.480
1.025
1.530
1.522
1.430
1.241
1.111
-
1.480
1.491
1.019
1.561
1.547
1.418
1.239
1.111
-
1.459
1.526
1.025
1.525
1.518
1.481
1.219
1.111
1.089
1.459
1.523
1.022
1.522
1.520
1.491
1.213
1.114
1.091
60.59
119.96
28.09
58.36
61.04
-
107.26
109.93
28.37
36.53
36.21
-
59.21
109.67
27.24
62.67
58.12
-
59.43
110.91
27.82
62.42
58.14
-
101.07
161.49
-
-166.50
-92.35
-
99.08
0.97
-156.68
0.68
101.15
-145.29
166.61
148.79
X=SiMe3- for Comp.(s) 3, 4 and 5 and H for other predicted Comp.(s).
(7a)
(7b)
(7c)
S4: The resonance forms of 3-amino-3-diazo-3,7-dimethyloct-6-enal (7). The structures were
calculated by theory (DFT) B3LYP/6-31G* method.
[TS]9
[TS]10
S5: The transition states ([TS]9 and [TS]10) of the N2 elimination from (6) and (8). The structures
were calculated by theory (DFT) B3LYP/6-31G* method.
S5: The bi-radical intermediates (13) and (14) to produce aziridine (15) (3R,4S) and (3S, 4S). The
structures were calculated by theory (DFT) B3LYP/6-31G* method.
S6: The structure of the singlet carbene intermediate (11). The structures were calculated by
theory (DFT) B3LYP/6-31G* method.
[TS]15 (from Geranial)
[TS]15’ (from Neral)
S7: The transition states ([TS]15 and [TS]15’) of the aziridines (15) formation. The structures were
calculated by theory (DFT) B3LYP/6-31G* method.
S8: The products of aziridine (15) (3R,4S) and (3S, 4S). The structures were calculated by theory
(DFT) B3LYP/6-31G* method.
S9: The diagram of the GC spectrum related to the GC-MS experimental part of this study. The
GC and GC-MS analysis was performed on a Perkin Elmer GC(Clarus680)-MS(Clarus-SQ8S)
instrument, injector 250ºC; temperature program: 70ºC (1 min), then 10ºC per min till 300ºC on an
Elite-5MS capillary column (0.25 μm thickness, 0.25mm diameter, 30m length). The ionization
energy for Mass spectra was 30eV.
S10: The mass spectrum of the aziridine derivative 15 (A, B and C) related to the experimental
part of this study. The retention times (RT) in GC-Mass experiment was 4.43, 8.29 and 9.20min
under the spectroscopy conditions. The GC and GC-MS analysis was performed on a Perkin
Elmer GC(Clarus680)-MS(Clarus-SQ8S) instrument, injector 250ºC; temperature program: 70ºC
(1 min), then 10ºC per min till 300ºC on an Elite-5MS capillary column (0.25 μm thickness,
0.25mm diameter, 30m length). The ionization energy for Mass spectra was 30eV.