Hydroalkylation of Alkynyl ethers via a Gold(I)-Catalyzed 1,5-Hydride Shift / Cyclization Sequence
Igor Dias Jurberg, Yann Odabachian, and Fabien Gagosz*
Laboratoire de Synthèse Organique, UMR 7652 CNRS / Ecole Polytechnique, 91128 Palaiseau, France.
Supporting Information
1H- and 13C-NMR Spectra of starting materials 1a-l, 7a-e, 10d-f, 12, 16 and 31
S-1
O
CO2Me CO2Me
8.0
1a
7.0
6.0
5.0
4.0
ppm (f1)
S-2
3.0
2.0
1.0
O
CO2Me CO2Me
200
1a
150
100
405(1a) ppm (f1)
S-3
50
0
D O
CO2Me CO2Me
8.0
12
7.0
6.0
5.0
4.0
ppm (f1)
S-4
3.0
2.0
1.0
D O
200
CO2Me CO2Me
12
150
100
ppm (f1)
S-5
50
0
D
CO2Me
O
CO2Me
8.0
16
7.0
6.0
5.0
4.0
ppm (f1)
S-6
3.0
2.0
1.0
D
200
O
CO2Me CO2Me
16
150
100
ppm (f1)
S-7
50
0
1b
O OAc AcO
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-8
3.0
2.0
1.0
1b
O OAc AcO
200
150
100
ppm (f1)
S-9
50
0
O
CO2Me CO2Me
8.0
1c
7.0
6.0
5.0
4.0
ppm (f1)
S-10
3.0
2.0
1.0
O
CO2Me CO2Me
1c
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-11
O
8.0
1d CO2Me CO2Me
7.0
6.0
5.0
4.0
ppm (f1)
S-12
3.0
2.0
1.0
O
1d CO2Me CO2Me
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-13
MeO2C O
8.0
1e CO2Me CO2Me
7.0
6.0
5.0
4.0
ppm (f1)
S-14
3.0
2.0
1.0
MeO2C O
1e CO2Me CO2Me
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-15
-
H
H
8.0
7.0
O
CO2Me CO2Me
6.0
1f
5.0
4.0
ppm (f1)
S-16
3.0
2.0
1.0
H
H
O
CO2Me CO2Me
1f
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-17
EtO2C
8.0
O
7.0
CO2Me CO2Me
6.0
1g
5.0
4.0
ppm (f1)
S-18
3.0
2.0
1.0
EtO2C
O
CO2Me CO2Me
1g
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-19
EtO2C
8.0
7.0
O
6.0
CO2Me CO2Me
1h
5.0
4.0
ppm (f1)
S-20
3.0
2.0
1.0
200
150
100
50
0
100
50
0
ppm (f1)
EtO2C
200
150
O
CO2Me CO2Me
1h
ppm (f1) S-21
O O
8.0
7.0
CO2Me CO2Me
6.0
1i
5.0
4.0
ppm (f1)
S-22
3.0
2.0
1.0
200
150
100
50
0
100
50
0
ppm (f1) O O
200
150
CO2Me CO2Me
1i
ppm (f1) S-23
O EtO2C
8.0 ppm (f1)
7.0
O
CO2Me CO2Me
6.0
1j
5.0
4.0
S-24
3.0
2.0
1.0
O EtO2C
O
CO2Me CO2Me
1j
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-25
Br
CO2Me
O
1k
CO2Me
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-26
3.0
2.0
1.0
Br
200
O
CO2Me
1k
CO2Me
150
100
ppm (f1)
S-27
50
0
O
CO2Me CO2Me
Ph
1l
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-28
3.0
2.0
1.0
O
CO2Me CO2Me
Ph
1l
200
150
100
ppm (f1)
S-29
50
0
MeO2C CO2Me 7a O
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-30
3.0
2.0
1.0
MeO2C CO2Me 7a O
200
150
100
ppm (f1)
S-31
50
0
MeO2C MeO2C 31 O
8.0
D
7.0
6.0
5.0
4.0
ppm (f1)
S-32
3.0
2.0
1.0
MeO2C MeO2C 31 O
200
150
D
100
ppm (f1)
S-33
50
0
MeO2C CO2Me 7b O
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-34
3.0
2.0
1.0
MeO2C CO2Me 7b O
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-35
MeO2C CO2Me 7c O
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-36
3.0
2.0
1.0
MeO2C CO2Me 7c O
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-37
MeO2C CO2Me 7d O CO2Et
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-38
3.0
2.0
1.0
MeO2C CO2Me 7d O CO2Et
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-39
MeO2C CO2Me 7e
O Br
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-40
3.0
2.0
1.0
MeO2C CO2Me 7e
O Br
200
150
100
ppm (f1)
S-41
50
0
MeO2C MeO2C 7f O
8.0
7.0
Me
6.0
5.0
4.0
ppm (f1)
S-42
3.0
2.0
1.0
MeO2C MeO2C 7f O
200
150
Me
100
ppm (f1)
S-43
50
0
CO2Me
MeO2C
O
7g
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-44
3.0
2.0
1.0
CO2Me
MeO2C
O
7g
200
150
100
ppm (f1)
S-45
50
0
CO2Et 10d O
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-46
3.0
2.0
1.0
CO2Et 10d O
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-47
CO2Et 10e O
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-48
3.0
2.0
1.0
CO2Et 10e O
200
150
100
50
0
200
150
100
50
0
ppm (f1)
ppm (f1) S-49
CO2Et 10f O
8.0
7.0
6.0
5.0
4.0
ppm (f1)
S-50
3.0
2.0
1.0
CO2Et 10f O
200
150
100
ppm (f1)
S-51
50
0
