Regio- and Stereoselective Allylindation of Alkynes Using InBr3 and Allylic. Silanes: Synthesis, Characterization, and Application of 1,4-Dienylindiums.
Supporting Information Regio- and Stereoselective Allylindation of Alkynes Using InBr3 and Allylic Silanes: Synthesis, Characterization, and Application of 1,4-Dienylindiums toward Skipped Dienes Yoshihiro Nishimoto1,*, Yi Junyi2, Tatsuaki Takata2, Akio Baba2, and Makoto Yasuda2,* 1 Frontier Research Base for Global Young Researchers Center for Open Innovation Research and Education (COiRE), Graduate School of Engineering, Osaka University 2 Department of Applied Chemistry, Graduate School of Engineering, Osaka University
Contents NOE Experiments ...............................................................................................................................2 NMR Spectra .......................................................................................................................................4
S1
NOE Experiments 1,4-dienylindium 3ha
S2
(Z)-(1-iodo-4-methylpenta-1,4-dien-2-yl)benzene (4ha)
S3
7 6 5 4 3
S4 45.82 36.44 31.87 29.43 29.38 29.22 26.99 22.67 21.78 14.13
13
8
77.32 77.00 76.68 76.19
9 2 3.40
3.02
2.05
2.02
1.05 1.08
1.00
5.92 4.83 4.75 4.33 2.87 2.18 2.16 2.14 1.65 1.43 1.42 1.41 1.39 1.38 1.36 1.33 1.30 14.0 1.29 1.28 1.25 1.23 0.90 0.88 0.87
1
113.03
149.37 142.45
NMR Spectra
(E)‐4‐(iodomethylene)‐2‐methyldodec‐1‐ene (4aa)
H NMR (400 MHz, in CDCl3)
PPM
1 0
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 -1
C NMR (100 MHz, in CDCl3)
PPM
0 -10
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
0
PPM 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
PPM
HMQC
8 7
7
6 5
6 5
4
4
S5
3
3
2
2
1 PPM
HMBC
1 PPM
(E)‐4‐(iodomethylene)‐2,7‐dimethyloct‐1‐ene (4ba)
1
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S6
(E)‐4‐(iodomethylene)‐2,6‐dimethylhept‐1‐ene (4ca)
2.04 1.01 3.04
1.00
1.04 1.00
2.02
6.05
2.87 2.10 2.08 1.95 1.94 1.92 1.90 1.88 1.87 1.85 1.65 0.94 0.92
4.84 4.74
H NMR (400 MHz, in CDCl3) 6.01
1
7
6
5
4
3
2
1
0
-1
77.49 77.32 77.00 76.68
113.15
C NMR (100 MHz, in CDCl3) 148.39 142.43
13
8
26.84 22.38 21.77
9
46.12 44.66
PPM
PPM 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
S7
0 -10
7 6 5 4 3
S8 47.33 42.06 29.93 26.29 26.01 21.96
13
8
77.32 77.00 76.68 76.04
9
113.68
2 1.02
2.00
2.00 0.92
1.01 1.01
0.97
4.06
6.02
1
142.82
151.77
5.83 4.87 4.77 2.81 2.62 2.60 2.59 2.59 2.57 2.56 1.79 1.78 1.75 1.70 1.67 1.61 1.60 1.57 1.36 1.36 1.32 1.29 1.27 1.26 1.23 1.23 1.19 1.18 1.16 1.15 1.14 1.13 1.12
(Z)‐(1‐iodo‐4‐methylpenta‐1,4‐dien‐2‐yl)cyclohexane (4da)
H NMR (400 MHz, in CDCl3)
PPM
1 0
C NMR (400 MHz, in CDCl3)
PPM
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
0 -10
(E)‐(3‐(iodomethylene)‐5‐methylhex‐5‐en‐1‐yl)benzene (4fa)
1
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S9
(E)‐7‐chloro‐4‐(iodomethylene)‐2‐methylhept‐1‐ene (4ga)
1
H NMR (400 MHz, CDCl3)
13
C NMR (100 MHz, CDCl3)
S10
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
0
PPM 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
PPM
HMQC
8
HMBC
PPM
7 6 5 4 3 2 1 PPM
7 6 5 4 3 2 1
S11
(Z)‐(1‐iodo‐4‐methylpenta‐1,4‐dien‐2‐yl)benzene (4ha)
1
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S12
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
0
PPM 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
PPM
HMQC
8 7
7
6 5
6 5
4
4
S13
3
3
2
2
1 PPM
HMBC
1 PPM
(Z)‐(1‐iodopenta‐1,4‐dien‐2‐yl)benzene (4hb) I
1 2
1
3
4 5
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S14
(Z)‐1‐iodo‐2,4‐diphenylpenta‐1,4‐diene (4hc)
1
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S15
(Z)‐(1‐iodo‐3,3‐dimethylpenta‐1,4‐dien‐2‐yl)benzene (4hd) I 1 2
3
4 5
1
H NMR (400 MHz, CDCl3)
13
C NMR (100 MHz, CDCl3)
S16
(Z)‐1‐iodo‐2,3‐diphenylpenta‐1,4‐diene (4he)
1
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S17
(Z)‐(4‐methyl‐2‐phenylpenta‐1,4‐dien‐1‐yl)indium(III) bromide (3ha)
1
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S18
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
0
PPM 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
PPM
HMQC
8
HMBC
PPM
7 6 5 4 3 2 1 PPM
7 6 5 4 3 2 1
S19
(Z)‐4‐methy‐1,2‐diphenylpenta‐1,4‐diene (5)
1 2 3
1
4
5
H NMR (400 MHz, in CDCl3)
13
C NMR (100 MHz, in CDCl3)
S20
S21
