of 77
Suppor
ting
Information
Iron-Catalyzed
Reductive
Cross-Coupling
of Alkyl
Electrophiles
with
Olefins
X. Tong,
Z.-P.
Yang,
C. E. Del Angel
Aguilar,
G. C. Fu*
1
Supporting
Information
Table of Contents
I.
General Information
S−2
II.
Iron
-Catalyzed Reductive Cross-Couplings and Hydroborations
S−3
III.
Observations during Reaction Development
S−14
IV.
Effect of Reaction Parameters
S−17
V.
Mechanistic Studies
S−19
VI.
Studies of Functional-Group Compatibility
S−29
VII.
NMR Spectra
S−30
2
I. General Information
Unless otherwise noted, reagents received from commercial suppliers were used as
received.
All reactions were performed under
an atmosphere of dry nitrogen.
Fe(OAc)
2
was purchased from Strem;
Xantphos
, D
2
SiPh
2
,
and
HSi(OEt)
3
w
ere
purchased from
Sigma
-
Aldrich;
Mg(OEt)
2
and HBpin
w
ere
purchased from Acros
.
All
solvents were
purified by passage through activated aluminum oxide in a solvent
-
purification
system
;
THF was purified
by passage through activated aluminum oxide in a solvent
-
purification
system and stored over molecular sieves under dry nitrogen.
Glassware was oven
-
dri
ed at 150
°C for a minimum of 12
h
, or
it was
flame
-
dried
utilizing a torch under high vacuum.
NMR spectra
were collected on a
Bruker
4
00 MHz
or a Varian 500 MHz
spectrometer at ambient temperature;
chemical shifts (
δ
) are reported in ppm
downfield
from
te
tramethylsilane, using the solvent resonance as the internal standard.
FT
-
IR
measurements were carried out on a Thermo Scientific Nicolet iS
5 FT
-
IR
spectrometer
equipped with an
iD5 ATR
a
ccessory
.
LC
-
MS were obtained on an Agilent 6
230
LC
-
TOF
system in electrospray ionization (ESI+) mode.
GC
-
MS
analyses were carried out on an
Agilent 6890N GC. Flash column chromatography was performed using silica gel
(SiliaFlash
®
P60, particle size 40
-
63
μm
, Silicycle).
Mössbauer spectra were recorded
at
77 K
on a spectrometer from SEE Co. (Edina, MN) operating in constant acceleration
mode in a transmission geometry
; t
he quoted isomer shifts are relative to the centroid of
the spectrum of a metallic foil of α
-
Fe at room temperature.
3
II. Iron
-
Catalyzed
Redu
ctive Cross
-
Couplings
and Hydroborations
(Figure
s
3
and 5
)
General Procedure 1 (GP
-
1).
In a nitrogen
-
filled glovebox, a 7
-
mL vial was charged
with a large stir bar and
a
small stir bar, followed by Fe(OAc)
2
(17 mg, 0.10 mmol, 10
mol%),
X
antphos (69 mg, 0.12 mmol, 12 mol%), and Mg(OEt)
2
(228 mg, 2.0 mmol, 2.0
equiv
). T
hen, T
HF (5.0 mL)
,
the
olefin (
1.0
mmol, 1.0
equiv
),
the
alkyl iodide (1.
5
mmol,
1.5
equiv
), and
HSi(OEt)
3
(0.
38
mL,
2.0
mmol, 2.0
equiv
;
Note:
HSi(OEt)
3
is hazardous
and should be handled with care
) w
ere
added.
The vial was capped
,
wrapped with
electrical tape
, and removed from
the glovebox
. The reaction mixture was
vigorously
stirred
at r.t.
for 24 h
, and then th
e mixture was diluted with hexan
e
s
and passed
through a pad of celite on top of silica, flushing with hexane
s
and
Et
2
O
. The
filtrate
was
concentrated
,
and
the residue was
purified
by
column chromatography.
General Procedure
2
(GP
-
2
).
GP
-
1
was followed
for
the reaction
itself
. After
the
reaction
was complete
,
t
he mixture was diluted with hexane
s
and passed through a pad
of celite on top of silica, flushing with hexane
s
and
Et
2
O
. The
filtrate
was concentrated
,
and the residue was
dissolved in
DCM (~10 mL). The
solution
was cooled to 0
°C
,
and
H
2
O
2
(
30% solution in water,
0.34 mL
) was added. The mixture was stirred vigorously
under air for 4
h at r.t.,
and then it
was washed with water, and the aqueous phase was
extracted
once
with
Et
2
O
. The organic phase was dried
over
Na
2
SO
4
and
concentrated,
and
the residue was
purified by column chromatography.
n
-
Undecyl
benzene
(
Figure 3, entries
1
and 18
).
[
1
]
The title compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d 1
-
octene
. The product
was purified by column chr
omatography on silica gel (
100%
hexanes).
Colorless oil.
Run 1: 169 mg, 73%. Run 2: 1
74
mg, 7
5
%.
Alternatively, the title compound was synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
cis
-
4
-
octene
.
Run 1:
118
mg,
51
%. Run 2:
123
mg,
53
%.
[
1
]
S. Kobayashi, H. Kuroda, Y. Ohtsuka, T. Kashihara, A. Masuyama, K. Watanabe,
Tetrahedron
2013
,
69
, 2251
2259.
1.5 equiv
alkyl
alkyl
Fe(OAc)
2
(10 mol%)
Xantphos (12 mol%)
Mg(OEt)
2
(2.0 equiv)
THF, r.t.
1
1
H
Si(OEt)
3
(2.0 equiv)
alkyl
I
alkyl
n
-Hex
Ph
4
1
H NMR (400 MHz, CDCl
3
)
δ
7.30
7.25 (m,
2
H), 7.18 (d,
J
= 7.1 Hz, 3H), 2.67
2.52
(m, 2H), 1.69
1.56 (m, 2H), 1.39
1.17 (m, 16H), 0.92
0.81 (m, 3H).
13
C NMR (101 MHz, CDCl
3
)
δ
143.0
, 128.4, 128.2, 125.5, 36.0, 31.9, 31.
6
, 29.7
2
, 29.68,
29.65, 29.6, 29.5, 29.
4
, 22.7, 14.1.
FT
-
IR (film):
3062, 3027,
2957,
2922, 2852,
1494, 1454,
744, 696
cm
-
1
.
MS (
GC
-
MS)
m/z
[M
]
+
calcd for C
17
H
28
:
232.
2
2
,
found:
232.22
,
147.11,
133.10, 92.08
.
Gram
-
scale reaction:
The reaction was
scaled up to 8.0 mmol (of olefin) and set up
according to
GP
-
1
,
except
that
a 250
-
mL flask was used
.
1.39 g, 75%.
Reaction with
7.
5 mol% Fe:
The procedure
for
the
gram
-
scale reaction
above was
followed,
using
Fe(OAc)
2
(104 mg, 0.60 mmol, 7.5 mol%),
Xantpho
s
(416 mg, 0.72 mmol,
9.0
mol%)
. 1.26 g, 68%.
(7,7
-
D
imethyloctyl)benzene
(
Figure 3, entry 2
).
The title compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
4,4
-
dimethylpent
-
1
-
ene
.
The product was purified by column chr
omatography on silica gel (100%
hexanes).
Colorless oil. Run 1: 156 mg, 72%. Run 2: 161 mg, 74%.
1
H NMR (400 MHz, CDCl
3
)
δ
7.32
7.24 (m, 2H), 7.18 (d,
J
= 7.3 Hz, 3H), 2.67
2.53
(m, 2H), 1.67
1.57 (m, 2H), 1.42
1.07 (m, 8H), 0.86 (s, 9H).
13
C NMR (
101 MHz, CDCl
3
)
δ
143.0, 128.4, 128.2, 125.6, 44.3, 36.0, 31.6, 30.5, 30.3
(overlapping signals), 29.4, 24.5.
FT
-
IR (film):
3027, 2928, 2856, 1605, 1495, 1466, 1393, 1248, 1030, 745, 696
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
16
H
26
:
218.20,
found:
218.21
, 203.17, 162.14, 147.10,
133.10, 91.07
.
(5
-
C
yclohexylpentyl)benzene
(
Figure 3, entr
ies
3
and 19
).
[
2
]
The title compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
vinylcyclohexane
.
The
product was purified by column chr
omatography on silica gel (100%
hexanes).
Colorless oil.
Run 1: 160 mg, 69%. Run 2: 156 mg, 68%.
[
2
]
G.
-
B. Lin, H.
-
Y. Zhao, L. Dai, T. Thiemann, H. Tashiro, M. Tashiro,
J. Chem. Res.
2009
,
9
, 578
581.
Ph
t
-Bu
Ph
5
Alternatively, the title compound was synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
ethylidenecyclohexane
.
Run 1:
106
mg,
46
%. Run 2:
101
mg,
44
%.
1
H NMR (400 MHz, CDCl
3
)
δ
7.29
7.24 (m, 2H), 7.21
7.06 (m, 3H), 2.60 (dd,
J
= 8.8,
6.8 Hz, 2H), 1.76
1.56 (m, 7H), 1.37
1.06 (m, 10H), 0.85 (qd,
J
= 10.9, 4.4 Hz, 2H).
13
C NMR (101 MHz, CDCl
3
)
δ
143.0, 128.4, 128.2, 125.5, 37.7, 37.5, 36.0, 33.5, 31.6, 29.7,
26.8, 26.7, 26.5.
FT
-
IR (film):
3026,
2919, 285
0
, 1495, 1448, 1030, 743, 696
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
1
7
H
2
6
:
230.20
,
found:
230.22
,
187.16, 147.12,
92.08
.
(6,6
-
D
imethylheptyl)benzene
(
Figure 3, entry 4
).
The title compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
t
-
butylethylene
.
The
product was purified by column chr
omatography on silica gel (100%
hexanes).
Colorless oil. Run 1:
115
mg,
56
%. Run 2:
117
mg,
57
%.
1
H NMR (400 MHz, CDCl
3
)
δ
7.35
7.26 (m, 2H), 7.18 (d,
J
= 7.3 Hz, 3H), 2.70
2.49
(m, 2H), 1.69
1.56 (m, 2H), 1.
35
1.19
(
m,
4H), 1.20
1.11 (m, 2H), 0.86 (s, 9H).
13
C NMR (101 MHz, CDCl
3
)
δ
143.0, 128.4, 128.2, 125.6, 44.2, 36.1, 31.6, 30.3
0
, 30.
28
,
29.4, 24.4.
FT
-
IR (film):
3027,
2929
, 2858, 1604, 1495, 1466, 1363, 1248,
743, 696
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
1
5
H
2
4
:
204.19
,
found:
204.20
, 189.17,
148.13, 91.07
.
(4
-
C
yclohexylbutyl)benzene
(
Figure 3, entry 5
).
[
3
]
The title compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
methylene
cyclohexane
.
The product was purified by column chr
omatography on silica gel (100%
hexanes).
Colorless oil. Run 1:
97
mg,
45
%. Run 2:
99
mg,
46
%.
1
H NMR (400 MHz, CDCl
3
)
δ
7.31
7.25 (m, 2H), 7.18 (d,
J
= 7.1 Hz, 3H), 2.70
2.52
(m, 2H), 1.74
1.54 (m, 7H), 1.38
1.28 (m, 2H), 1.26
1.08 (m, 6H), 0.86 (tt,
J
= 11.5, 6.2
Hz, 2H).
13
C NMR (101 MHz, CDCl
3
)
δ
143.0, 128.4, 128.2, 125.5, 37.6, 37.4, 36.0, 33.5, 31.9, 26.8,
26.6, 26.5.
[
3
]
J. Zhou, G. C. Fu,
J. Am. Chem.
Soc.
2003
,
125
, 12527
12530.
t
-Bu
Ph
Ph
6
FT
-
IR (film):
2920,
2850, 1496, 1448, 1030, 744, 696, 496
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
1
6
H
2
4
:
216.19
,
found:
216.21
, 187.16, 173.14, 133.09,
120.09, 105.07, 92.08
.
tert
-
B
utyldimethyl((9
-
phenylnonyl)oxy)silane
(
Figure 3, entry
6
).
The title
compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
tert
-
butyl(hex
-
5
-
en
-
1
-
yloxy)dimethylsilane
.
The product was purified by column
chr
omatography on silica gel (
5
20
%
DCM in
hexanes).
Colorless oil. Run 1:
230
mg,
69
%. Run 2:
227
mg,
68
%.
1
H NMR (400 MHz, CDCl
3
)
δ
7.30
7.26 (m,
2
H), 7.20
7.12 (m, 3H), 3.59 (t,
J
= 6.6
Hz, 2H), 2.72
2.49 (m, 2H), 1.69
1.56 (m, 2H), 1.49 (q,
J
= 6.9 Hz, 2H), 1.40
1.22 (m,
1
0
H), 0.89 (s, 9H), 0.05 (s, 6H).
13
C NMR (101 MHz,
CDCl
3
)
δ
143.0, 128.4, 128.2, 125.6, 63.4, 36.0, 32.9, 31.5, 29.6,
29.47, 29.45, 29.3, 26.0, 25.8, 18.4,
5.2.
FT
-
IR (film):
3068, 3026,
292
7, 2854, 1463,
1387,
1253,
1095,
774,
745, 661
cm
-
1
.
MS (GC
-
MS)
m/z
[M
-
t
-
Bu
]
+
calcd for
C
17
H
29
OSi
:
277.2
0
,
found:
277.22
,
259.21, 207.04,
201.18, 165.08, 117.07, 91.07, 75.05
.
2
-
(8
-
P
henyloctyl)
-
1,3
-
dioxane
(
Figure 3, entry
7
).
The title compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
2
-
(pent
-
4
-
en
-
1
-
yl)
-
1,3
-
dioxane
.
The product was purified by column chr
omatography on silica gel (
0%
10%
DCM in hexane, followed by 0%
5% Et
2
O
+
10% DCM in hexanes
).
Colorless oil. Run
1: 2
05
mg
, 74
%. Run 2:
212
mg,
77
%.
1
H NMR (500 MHz, CDCl
3
)
δ
7.39
7.29 (m, 2H), 7.30
7.11 (m, 3H), 4.55 (t,
J
= 5.2
Hz, 1H), 4.15 (ddt,
J
= 10.4, 5.0, 1.4 Hz, 2H), 3.91
3.72 (m, 2H), 2.78
2.56 (m, 2H), 2.13
(dtt,
J
= 13.4, 12.5, 5.0 Hz, 1H), 1.78
1.59 (m, 4H), 1.49
1.28 (m, 11H).
13
C NMR (101 MHz, CDCl
3
)
δ
143.0, 128.4, 128.2, 125.6, 102.5, 66.9, 36.0, 35.3, 31.5,
29.49, 29.45, 29.4, 29.3, 25.9, 24.0.
FT
-
IR (film):
3063, 3030, 2925, 1456, 1377, 1240,
1143,
1078,
698, 474
cm
-
1
.
MS (
GC
-
MS)
m/z
[M
]
+
calcd for
C
18
H
2
8
O
2
:
276.21
,
found:
276.24
, 200.16,
131.09, 104.07,
91.07, 87.07
.
Ph
OTBS
3
Ph
O
3
O
7
4,4,5,5
-
T
etramethyl
-
2
-
(4
-
((8
-
phenoxyoctyl)oxy)phenyl)
-
1,3,2
-
dioxaborolane
(
Figure
3, entry
8
).
The title compound was
synthesized according to
GP
-
1
,
scaled down to
0.5
mmol of
olefin
,
from
(3
-
iodoprop
oxy
)benzene
an
d
4,4,5,5
-
tetramethyl
-
2
-
(4
-
(pent
-
4
-
en
-
1
-
yloxy)phenyl)
-
1,3,2
-
dioxaborolane
.
The product was purified by column
chr
omatography on silica gel (0%
2
0% DCM in hexane
s
, followed by
0
%
5%
EtO
Ac
+
2
0% DCM in hexanes
).
White solid
. Run 1:
111
mg,
52
%. Run 2:
119
mg,
56
%.
1
H NMR (400 MHz, CDCl
3
)
δ
7.83
7.55 (m, 2H), 7.38
7.23 (m,
2
H), 7.13
6.75 (m,
5H), 3.97 (dt,
J
= 9.8, 6.5 Hz, 4H), 1.86
1.70 (m, 4H), 1.53
1.35 (m,
8
H), 1.33 (s, 12H).
13
C NMR (101 MHz, CDCl
3
)
δ
161.7, 159.1, 136.5, 129.4, 120.5, 114.5, 113.9, 83.5, 67.8,
67.7, 29.3
2
, 29.
29
, 29.2, 26.02, 25.98, 24.9
(
overlappin
g
signals)
.
FT
-
IR (film):
2976, 2928, 1604, 139
5,
1359,
1318, 1275, 1077, 962, 831, 787, 736
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
26
H
37
B
O
4
:
424.29
,
found:
424.
22
,
330.92, 252.99,
206.99, 190.95, 133.98, 93.98
.
(8
R
,9
S
,13
S
,14
S
)
-
13
-
M
ethyl
-
3
-
((8
-
phenyloctyl)oxy)
-
6,7,8,9,11,12,13,14,15,16
-
decahydrospiro[cyclopenta[a]phenanthrene
-
17,2'
-
[1,3]dioxolane]
(
Figure 3, entry 9
).
The title compound was
synthesized according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d
(8
R
,9
S
,13
S
,14
S
)
-
13
-
methyl
-
3
-
(pent
-
4
-
en
-
1
-
yloxy)
-
6,7,8,9,11,12,13,14,15,16
-
decahydrospiro[cyclopenta[a]phenanthrene
-
17,2'
-
[1,3]dioxolane]
.
The product was
purified by column chr
omatography on silica gel (0%
10% DCM in hexane
s
, followed
by 0%
8
% EtO
Ac
+
10% DCM in hex
anes
).
Colorless oil. Run 1:
365
mg, 7
3
%. Run 2:
355
mg, 7
0
%
.
1
H NMR (400 MHz, CDCl
3
)
δ
7.35
7.26 (m, 2H), 7.22
7.09 (m, 4H), 6.69 (dd,
J
= 8.6,
2.7 Hz, 1H), 6.65
6.58 (m, 1H), 4.02
3.85 (m, 6H), 2.91
2.75 (m, 2H), 2.67
2.55 (m,
2H), 2.38
2.17 (m, 2H), 2.
10
1.95
(
m
, 1H), 1.95
1.69 (m, 6H), 1.69
1.49 (m, 5H), 1.49
1.28 (m, 1
1
H), 0.88 (
s
, 3H).
PhO
O
BPin
3
Ph
O
Me
H
H
H
O
O
2
8
13
C NMR (101 MHz, CDCl
3
)
δ
157.0, 142.9, 138.0, 132.5, 128.4, 128.2, 126.3, 125.6,
119.5, 114.5, 112.0, 67.9, 65.3, 64.6, 49.4, 46.2, 43.7, 39.1, 36.0, 34.3, 31.5, 30.8, 29.8, 29.4,
29.34, 29.32, 29.27, 27.0, 26.2, 26.1, 22.4, 14.4.
FT
-
IR (film):
3027, 2929, 2856, 1608,
1497, 1454,
1308, 1255, 1161, 1104, 1067,
962
, 909,
747
cm
-
1
.
(8
-
M
ethoxyoctyl)cyclohexane
(
Figure 3, entry
10
).
The title compound was
synthesized according to
GP
-
2
from
(2
-
iodoethyl)cyclohexane
an
d
6
-
methoxyhex
-
1
-
ene
.
The product was purified by column chr
omatography on silica gel (
5
%
10
% Et
2
O in
hexanes
).
Colorless oil. Run 1:
161
mg, 7
1
%. Run 2:
158
mg, 7
0
%
.
1
H NMR (400 MHz, CDCl
3
)
δ
3.36 (t,
J
= 6.7 Hz, 2H), 3.33 (s, 3H), 1.75
1.50 (m, 7H),
1.39
1.08 (m, 16H), 0.94
0.76 (m, 2H).
13
C NMR (101 MHz, CDCl
3
)
δ
73.0, 58.6, 37.7, 37.6, 33.5, 29.9, 29.7, 29.6, 29.5, 26.9,
26.8, 26.5, 26.1.
FT
-
IR (film):
2978, 2920, 2850, 1448
, 1386, 1129, 948, 72
2
cm
-
1
.
MS (
GC
-
MS)
m/z
[M
]
+
calcd for
C
1
5
H
3
0
O
:
2
26
.
2
3
,
found:
226.26
, 194.26, 166.20, 152.18,
138.17,
124.15, 109.13, 96.14, 82.13
.
tert
-
B
utyl((11
-
fluoroundecyl)oxy)dimethylsilane
(
Figure 3, entry 11
).
The title
compound was
synthesized according to
GP
-
1
from
1
-
fluoro
-
5
-
iodopentane
an
d
tert
-
butyl(hex
-
5
-
en
-
1
-
yloxy)dimethylsilane
.
The product was purified by column
chr
omatography on silica gel (5%
25% DCM in hexanes
).
Colorless oil. Run 1: 160
mg, 53%. Run 2: 164 mg, 54%.
1
H
NMR (400 MHz, CDCl
3
)
δ
4.43 (dt,
J
= 47.4, 6.2 Hz, 2H), 3.59 (t,
J
= 6.6 Hz, 2H),
1.78
1.60 (m, 2H), 1.50 (q,
J
= 6.8 Hz, 2H), 1.41
1.26 (m, 14H), 0.89 (s, 9H), 0.05 (s, 6H).
13
C NMR (101 MHz, CDCl
3
)
δ
84.3 (d,
J
= 163.9 Hz), 63.4, 32.9, 30.42 (d,
J
= 19.3 Hz),
29.6, 29.504, 29.496, 29.4, 29.3, 26.0, 25.8, 25.2 (d,
J
= 5.5 Hz), 18.4,
5.2.
19
F NMR (282 MHz, CDCl
3
)
δ
12.00 (tt,
J
= 47.0, 24.6 Hz).
FT
-
IR (film):
2927, 2855, 1463, 1388, 1253, 1098, 833, 773, 661
cm
-
1
.
MS (
GC
-
MS)
m/z
[M
-
t
-
Bu
]
+
calcd for
C
13
H
28
F
O
Si
:
247.19
,
found:
247.19
, 157.13, 143.10,
133.06, 129.08, 115.07, 111.12, 107.04, 97.12
.
OMe
4
OTBS
4
F
9
tert
-
B
utyldimethyl((10,10,10
-
trifluorodecyl)oxy)silane
(
Figure 3, entry 12
).
The title
compound was
synthesized according to
GP
-
1
from
1,1,1
-
trifluoro
-
4
-
iodobutane
an
d
tert
-
butyl(hex
-
5
-
en
-
1
-
yloxy)dimethylsilane
.
The product was purified by column
chr
omatography on silica gel (5%
15% DCM in hexanes
).
Colorless oil. Run 1: 169
mg, 52%. Run 2: 165 mg, 51%.
1
H NMR (400 MHz, CDCl
3
)
δ
3.60 (t,
J
= 6.6 Hz, 2H), 2.15
1.88 (m, 2H), 1.62
1.45
(m, 4H), 1.42
1.18 (m, 10H), 0.89 (s, 9H), 0.05 (s, 6H).
13
C NMR (101 MHz, CDCl
3
)
δ
127.3 (q,
J
= 276.2 Hz)
, 63.3,
33.7 (q,
J
= 28.2 Hz)
, 32.9,
29.3 (overlapping signals), 29.1, 28.8, 26.0, 25.8,
21.8 (q,
J
= 2.9 Hz),
18.4,
5.3.
19
F NMR (282 MHz,
CDCl
3
)
δ
-
66.44 (t,
J
= 11.0 Hz)
FT
-
IR (film):
2929, 2857, 1471, 1387, 1254, 1140, 833, 774, 656
cm
-
1
.
MS (
GC
-
MS)
m/z
[M
-
t
-
Bu
]
+
calcd for
C
12
H
24
F
3
O
Si
:
269.15
,
found:
269.18
, 249.19,
229.18, 175.17, 155.16,
133.12, 119.10, 113.12, 107.08
.
1
-
C
hloro
-
10
-
methoxydecane
(
Figure 3, entry
1
3
).
The title compound was
synthesized according to
GP
-
2
from
4
-
chloro
-
1
-
iod
o
butane
an
d
6
-
methoxyhex
-
1
-
ene
.
The product was purified by column chr
omatography on silica gel (5% Et
2
O in
hexanes
).
Colorless oil. Run 1: 1
46
mg, 71%. Run 2: 1
34
mg,
65
%
.
1
H NMR (400 MHz, CDCl
3
) δ 3.53 (t,
J
= 6.7 Hz, 2H), 3.36 (t,
J
= 6.6 Hz, 2H), 3.33 (s,
3H), 1.76 (dt,
J
= 14.8, 6.8 Hz, 2H), 1.55 (dt,
J
= 7.9, 6.4 Hz, 2H), 1.42 (dq,
J
= 14.1, 6.5 Hz,
2H), 1.29 (d,
J
= 2.8 Hz, 10H).
13
C NMR (101 MHz, CDCl
3
) δ 7
3.0
, 58.
6
, 45.2, 32.
7
, 29.
7
, 29.47, 29.45, 29.
4
, 28.
9
, 26.
9
,
26.1.
FT
-
IR (film):
2926, 2854, 1462, 1387, 1118, 723, 652
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
11
H
23
Cl
O:
206.14
,
found:
206.
19,
205.18,
174.11,
146.08, 118.06, 104.04, 97.11, 83.10
.
2
-
(9
-
M
ethoxynonyl)furan
(
Figure 3, entry 14
).
The title compound was
synthesized
according to
GP
-
1
from
2
-
(3
-
iodopropyl)furan
an
d
6
-
methoxyhex
-
1
-
ene
.
The product
was purified by column chr
omatography on silica gel (
10
%
20
%
DCM
in hexanes
F
3
C
OTBS
4
Cl
OMe
4
OMe
4
O
10
followed by 0
%
25% EtOAc in hexanes
).
Colorless oil. Run 1:
164
mg, 7
3
%. Run 2:
160
mg,
71
%
.
1
H NMR (400 MHz, CDCl
3
) δ 7.29 (dd,
J
= 1.9, 0.9 Hz, 1H), 6.27 (dd,
J
= 3.1, 1.9 Hz,
1H), 5.96 (dt,
J
= 3.0, 0.9 Hz, 1H), 3.36 (td,
J
= 6.7, 0.8 Hz, 2H), 3.33 (d,
J
= 0.8 Hz, 3H), 2.65
2.56 (m, 2H), 1.68
1.51 (m,
4
H), 1.39
1.25 (m, 1
0
H).
13
C NMR (101 MHz, CDCl
3
) δ 156.6, 140.6, 110.0, 104.5,
73.0,
58.6, 29.
7
, 29.48, 29.47,
29.3, 29.
2
, 28.03, 27.98, 26.1.
FT
-
IR (film):
3120, 2926, 2854,
1596, 1507, 1458, 1387, 1
118, 1006, 795
cm
-
1
.
MS (
GC
-
MS)
m/z
[M
]
+
calcd for
C
1
4
H
2
4
O
2
:
2
24
.1
8
,
found:
224.19
,
207.12, 163.08, 149.09,
135.08, 123.06, 107.06, 95.07, 81.06
.
1
-
(9
-
M
ethoxynonyl)
-
1
H
-
indole
(
Figure 3, entry
1
5
).
The title compound was
synthesized according to
GP
-
1
from
N
-
(3
-
iodopropyl)
indole
an
d
6
-
methoxyhex
-
1
-
ene
.
The product was purified by column chr
omatography on silica gel (10%
3
0
%
DCM in
hexanes followed by
2
0
%
3
5% Et
2
O in hexanes
).
Colorless oil. Run 1:
172
mg,
6
3%.
Run 2:
168
mg,
62
%
.
1
H NMR (400 MHz, CDCl
3
)
δ
7.63 (dt,
J
= 7.9, 1.0 Hz, 1H), 7.34 (dd,
J
= 8.3, 1.0 Hz,
1H), 7.20 (ddd,
J
= 8.2, 6.9, 1.2 Hz, 1H), 7.15
7.03 (m, 2H), 6.48 (dd,
J
= 3.1, 0.8 Hz, 1H),
4.11 (t,
J
= 7.1 Hz, 2H), 3.36 (d,
J
= 6.6 Hz, 2H), 3.33 (s, 3H), 1.93
1.77 (m, 2H), 1.68
1.47
(m, 2H), 1.29 (qd,
J
= 8.7, 5.5, 4.5 Hz, 10H).
13
C NMR (101 MHz, CDCl
3
) δ 135.9, 128.
6
, 127.
8
, 121.
3
, 120.9, 119.1, 109.
4
, 100.8, 72.9,
58.
6
, 46.4, 30.
3
, 29.6, 29.44,
29.40, 29.
2
, 27.0, 26.1.
FT
-
IR (film):
2926, 2853, 1511, 1463, 1314, 1116, 762, 736, 425
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
1
8
H
2
7
N
O:
273.
21
,
found:
273.23
, 258.21, 242.21,
228.20, 172.11, 158.09, 130.06, 117.05
.
tert
-
B
utyldimethyl((9
-
(thiophen
-
2
-
yl)nonyl)oxy)silane
(
Figure 3, entry
1
6
).
The
title compound was
synthesized according to
GP
-
1
from
2
-
(3
-
iodopropyl)thiophene
an
d
tert
-
butyl(hex
-
5
-
en
-
1
-
yloxy)dimethylsilane
.
The product was purified by column
N
OMe
4
OTBS
4
S
11
chr
omatography on silica gel (
0
%
15
% DCM in hexanes
).
Colorless oil. Run 1:
229
mg, 6
7
%. Run 2:
234
mg, 6
9
%
.
1
H NMR (400 MHz, CDCl
3
) δ 7.10 (dd,
J
= 5.1, 1.2 Hz, 1H), 6.91 (dd,
J
= 5.1, 3.4 Hz,
1H), 6.77 (dq,
J
= 3.3, 1
.0 Hz, 1H), 3.59 (t,
J
= 6.6 Hz, 2H), 2.85
2.75 (m, 2H), 1.72
1.61
(m, 2H), 1.49 (q,
J
= 6.8 Hz, 2H), 1.39
1.27 (m, 1
0
H), 0.89 (s,
9
H), 0.05 (s, 6H).
13
C NMR (101 MHz, CDCl
3
) δ 145.9, 126.6, 123.9, 122.7, 63.3, 32.9, 31.8, 29.9, 29.5, 29.4,
29.3, 29.1, 26.0, 25.8, 18.4,
5.2.
FT
-
IR (film):
2927, 2854, 1463, 1253, 1096, 833, 773, 688
cm
-
1
.
MS (GC
-
MS)
m/z
[
M
-
t
-
Bu
]
+
calcd for C
1
5
H
27
O
SSi
:
283.16
,
found:
283.18
, 265.17, 207.14,
171.04, 151.07,
97.03, 75.07
.
n
-
Nonylbenzene
(
Figure 3, entry
17
).
[
4
]
The title compound was
synthesized
according to
GP
-
1
from
(3
-
iodopropyl)benzene
an
d trans
-
2
-
hexene
.
The product was
purified by column chr
omatography on silica gel (100%
hexanes).
Colorless oil. Run 1:
114 mg, 56%. Run 2: 115 mg, 56%.
1
H NMR (400 MHz, CDCl
3
)
δ
7.30
7.26 (m, 2H), 7.18 (d,
J
= 7.2 Hz, 3H), 2.66
2.56
(m, 2H), 1.66
1.55 (m, 2H), 1.36
1.21 (m, 12H), 0.92
0.82 (m, 3H).
13
C NMR (101 MHz, CDCl
3
)
δ
143.0, 128.4, 128.2, 125.5, 36.0, 31.9, 31.6, 29.6, 29.5,
29.
37
, 29.
35
, 22.7, 14.1.
FT
-
IR (film):
3063, 3024, 2923, 2853, 1496,
1455, 744, 696
cm
-
1
.
MS (GC
-
MS)
m/z
[M]
+
calcd for C
15
H
24
:
204.19,
found:
204.19
, 161.13, 147.14, 133.09,
105.08, 92.08
.
General Procedure 3 (GP
-
3).
In a nitrogen
-
filled glovebox, a 7
-
mL vial was charged
with a large stir bar and
a
smal
l
stir bar, followed by Fe(OAc)
2
(17 mg, 0.10 mmol, 10
mol%),
Xantphos
(69 mg, 0.12 mmol, 12 mol%), and Mg(OEt)
2
(228 mg, 2.0 mmol, 2.0
equiv
). THF (5.0 mL) was added, a
nd the mixture was stirred vigorously for
1
0 min.
Then,
the
olefin (0.22 mL, 1.0 mmol, 1.0
equiv
) and p
inacolborane
(0.29 mL, 2.0 mmol,
[
4
]
M. Piber, A. E. Jensen, M. Rottländer, P. Knochel,
Org. Lett.
1999
,
1
, 1323
1326.
Ph
Me
R
1
R
2
Fe(OAc)
2
(10 mol%)
Xantphos (12 mol%)
Mg(OEt)
2
(2.0 equiv)
THF, 35 °C
(2.0 equiv)
R
1
R
2
pinB
H
Bpin