Gold(i)-catalyzed Claisen rearrangement of allenyl vinyl ethers; Synthesis of substituted 1,3-dienes

Article abstract of DOI:10.1039/c1ob06297b

Synthesis of substituted 1,3-dienes was achieved via gold(i)-catalyzed Claisen rearrangement of allenyl vinyl ethers. The N-heterocyclic carbene gold chloride catalyst (IPrAuCl) was superior in terms of activity and selectivity and afforded the 3,3-product in excellent yields. A proposed cation-π inter-action played a significant role in affecting the reaction rate.

Full text of DOI:10.1039/c1ob06297b

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Gold (I)-Catalyzed Claisen Rearrangement of Allenyl Vinyl Ethers;
Synthesis of Substituted 1,3-Dienes
Marie E. Krafft,* Kassem M. Hallal, Dinesh V. Vidhani, John W. Cran
Supporting Information
General Information
Unless otherwise noted all commercial materials were used without further purification.
2 2 2
Dichloromethane (CH Cl ), Tetrahydrofuran (THF), and diisopropyl amine (i-Pr NH) were
purchased from J.T.Baker and distilled prior to use. Methanol was purchased from EMD and was
used without further purification. 1,4-dioxane was obtained from ACROS organics and was used
without purification. Ethyl vinyl ether, copper bromide (CuBr), mercuric acetate (Hg(OAc)
dihydropyran, silverhexafluoroantimonate (AgSbF ), silver triflate (AgOTf), silvertetra-
fluoroborate (AgBF ), silvercarbonate (Ag CO ), silverperchlorate (AgClO ). (Chloro[1,3-
bis(2,6-diisopropylphenyl)imidazol-2-ylidene]gold(I) (IPrAuCl) was purchased from Strem
chemicals and AuClPPh and all other gold catalysts were purchased from Aldrich.
2
),
6
4
2
3
4
3
Thin-Layer chromatographic (TLC) analysis of the reaction was performed using Merck silica
gel 60 F254 TLC plates and was visualized by anisaldehyde staining and UV. Flash column
chromatography was performed using Merck 60 silica gel (230-400 mesh) and Alumina (80-200
1
13
mesh). H and C NMR spectra were recorded with Bruker DRX-500 and 600 spectrometers
and referenced to CDCl or C . Mass spectral data were obtained via the mass spectrometry
3
6 6
D
lab facility at Florida State University. Infrared (IR) spectra were recorded as thin films on
sodium chloride plates using a Perkin‐Elmer FT‐IR Paragon 1000 Fourier Transform
–
1
spectrometer with frequencies given in reciprocal centimeters (cm ).
Propargylic alcohols were prepared by the addition of ethynylmagnesium bromide to the
1
corresponding aldehyde. Allenols were prepared according to Crabbe’ homologation method.
2
The allenyl vinyl ethers were prepared according to Yamamoto’s procedure. Spectroscopic data
3
4
for compounds B, D, were previously reported.
Reported yields refer to isolated yields of pure material as determined by spectroscopic
analysis.
1

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General procedure for synthesis of allenyl vinyl ethers
2
Vinyl ethers were prepared according to the method of Yamamoto, the allenyl alcohol was
dissolved in ethyl vinyl ether (0.1M) and then mercuric acetate (0.66 equiv.) was added. The
reaction mixture was stirred at room temperature overnight. Potassium carbonate was added to
the reaction mixture and the product was extracted with diethyl ether, the organic layer was dried
over sodium sulfate and then the product was purified using column chromatography with
hexane as an eluent.
Synthesis of (1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1a). (1-(vinyloxy)buta-2,3-dien-1-
yl)benzene was prepared according to the same procedure used for the synthesis of allenyl vinyl
ethers. The crude mixture was purified by flash chromatography using an alumina column and
1
hexane as an eluent and afforded the allenyl vinyl ether in 66% yield as a colorless oil: H NMR
(
500 MHz, CDCl
3
) δ 7.40 – 7.27 (m, 5H), 6.44 (dd, J = 14.2, 6.7 Hz, 1H), 5.38 (ddd, J = 7.8,
.5, 6.5 Hz, 1H), 5.32 (ddd J = 7.8, 1.55, 1.45 Hz, 1H), 4.93 (δobs) (ABdd, JAB = 11 Hz, J = 6.5,
.55 Hz, ∆υ = + 23.5 Hz, 1H; ABdd, JAB = 11 Hz, J = 6.5, 1.45 Hz, ∆υ = - 23.5 Hz, 1H), 4.39
6
1
1
3
(
dd, J = 14.2, 1.8 Hz, 1H), 4.11 (dd, J = 6.7, 1.8 Hz, 1H); C NMR (126 MHz, CDCl
3
) δ 208.72,
-
1
1
1
1
50.08, 140.15, 128.64, 128.09, 126.51, 92.52, 90.11, 79.54, 77.35; IR (cm ) 1617.64, 1636.78,
+
+
956.06, 2894.81, 3031.30, 3064.35; HRMS (EI ) calc’d for [C12
H
12O] : m/z 172.08882, found
72.08888.
Synthesis of 1-chloro-4-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1b). 1-chloro-4-(1-
vinyloxy)buta-2,3-dien-1-yl)benzene was prepared according to the same procedure used for the
(
synthesis of allenyl vinyl ethers. The crude mixture was purified by flash chromatography using
an alumina column and hexane as an eluent and the allenyl vinyl ether was obtained in 75% yield
1
as a colorless oil: H NMR (500 MHz, CDCl
3
) δ 7.38 – 7.28 (m, 2H), 7.12 – 6.97 (m, 2H), 6.42
(dd, J = 14.2, 6.7 Hz, 1H), 5.33 (ddd, J = 7.5, 6.3, 6.3 Hz, 1H), 5.28 (d, J = 7.5 Hz, 1H), 4.86
(δobs) (ABdd, JAB = 11.5 Hz, J = 6.3, 1.4 Hz, ∆υ = + 21.82 Hz, 1H; ABdd, JAB = 11.5 Hz, J =
2

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6
.3, 1.2 Hz, ⊗ = - 21.82 Hz, 1H), 4.37 (dd, J = 14.2, 1.9 Hz, 1H), 4.11 (dd, J = 6.7, 1.9 Hz, 1H);
1
3
C NMR (126 MHz, CDCl
3
) δ 208.87, 150.01, 138.87, 133.82, 128.78, 127.90, 92.29, 90.42,
-
1
+
7
8.76, 77.64; IR (cm ) 1617.39, 1637.5, 1956.21, 2891.34, 2988.25, 3117.38; HRMS (EI )
+
calc’d for [C12
H
11OCl] : m/z 206.04985, found 206.05019.
Synthesis of (3-cyclohexylidene-1-(vinyloxy)allyl)benzene (1c) from propargyl alcohol A
OH
OTHP
OTHP
DHP, PPTS
DCM
BuLi, PhCHO
OH
Ph
THF, -78ºC
3-4 h
16 h, 95%
7
5%
A
B
C
D
LiAlH4
Et O, 2 h
2
7
5%
O
HO
Hg(OAc) , 55%
2
Ph
Ph
O
1c
Synthesis of 1c began with THP protection of propargylic alcohol A giving rise to the THP-
3
protected alcohol B in 95% yield. Treatment of ether B with butyllithium and benzaldehyde led
to the formation of the mono-protected diol C in 75% yield. Reduction of C using lithium
4
aluminum hydride gave allenyl alcohol D in 75% yield. Allenyl alcohol D was then converted
into vinyl ether 1c using ethyl vinyl ether and mercuric acetate.
Synthesis of 1-phenyl-3-(1-((tetrahydro-2H-pyran-2-yl)oxy)cyclohexyl)prop-2-yn-1-ol, C.
1
-phenyl-3-(1-((tetrahydro-2H-pyran-2-yl)oxy)cyclohexyl)prop-2-yn-1-ol
C
was prepared
5
according to the procedure of Cheung. Treatment of B with butyllithium and benzaldehyde led
to the formation of the mono-protected diol C in 75% yield. The crude mixture was purified by
flash chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 75 % yield as a yellow
1
oil: H NMR (500 MHz, C
6
D
6
) δ 7.62-7.57 (m, 2H), 7.19-7.14 (m, 2H), 7.09-7.04 (m, 1H), 5.48-
5
1
.41(m,2H), 3.96-3.88 (m, 1H), 3.44-3.36 (m, 1H), 2.2(s, 1H), 2.02-1.94 (m, 1H), 1.91-1.81 (m,
1
3
H), 1.8-1.54 (m, 8H), 1.4-1.21 (m,4H), 1.195-1.10 (m, 1H); C NMR (126 MHz, C
6 6
D )
3

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δ128.28, 127.98, 127.80, 126.65, 94.94, 74.61, 64.23, 62.09, 38.81, 31.92, 25.58, 25.37, 23.06,
+
+
1
25 3
9.64; HRMS (EI ) calc’d for [C20H O ] : m/z 313.18038, found 313.18201.
Synthesis of (3-cyclohexylidene-1-(vinyloxy)allyl)benzene (1c). (3-cyclohexylidene-1-
vinyloxy)allyl)benzene was prepared according to the same procedure used for the synthesis of
(
allenyl vinyl ethers. The crude mixture was purified by flash chromatography using an alumina
column and hexane as an eluent and afforded the allenyl vinyl ether in 60% yield as a colorless
1
oil: H NMR (500 MHz, CDCl
3
) δ 7.37 – 7.34 (m, 2H), 7.17-7.13 (m, 2H), 7.08-7.04 (m, 1H),
6
1
4
8
3
2
.44 (dd, J = 14.2, 6.7 Hz, 1H), 5.38 – 5.34 (m, 1H), 5.25 (d, J = 6.76 Hz, 1H), 4.5 (dd, J = 14.2,
.6 Hz, 1H), 4.06 (dd, J = 6.6, 1.6 Hz, 1H), 2.06-1.9 (m, 4H), 1.44-1.35 (m, 2H), 1.3-1.17 (m,
1
3
H); C NMR (126 MHz, CDCl
3
) δ 199.71, 150.8, 141.6, 128.48, 127.71, 126.88, 105.2, 92,
-
1
9.7, 80.6, 31.5, 27.3, 26.2 ; IR (cm ) 1614.55, 1635.19, 1967.28, 2854.24, 2887.73, 2928.33,
+
+
030.09, 3063.90, 3086.76, 3116.01; HRMS (EI ) calc’d for [C17
H
20O] : m/z 240.15142, found
40.15116.
Synthesis of 4-(vinyloxy)nona-1,2-diene (1d). 4-(vinyloxy)nona-1,2-diene was prepared
according to the same procedure used for the synthesis of allenyl vinyl ethers. The crude
mixture was purified by flash chromatography using an alumina column and hexane as an eluent
1
and afforded the allenyl vinyl ether in 60% yield as a colorless oil: H NMR (500 MHz, C
6
D
6
) δ
6
.35 (dd, J = 14.2, 6.6 Hz, 1H), 5.13 (ddd, J = 6.7, 6.6, 6.6 Hz, 1H), 4.86 (δobs) (ABdd, JAB =11,
J = 6.7, 1.55 Hz, ∆υ = + 15.18, 1H; ABdd, JAB =11, J = 6.3, 1.55 Hz, ∆υ = - 15.18, 1H), 4.3 (dd,
J = 14.1, 1.5 Hz, 1H), 4.15 (ddd, J = 6.7, 1.5, 1.5 Hz, 1H), 4.05 (dd, J = 6.6, 1.5 Hz, 1H), 1.74 –
1
3
1
.61 (m, 1H), 1.51 (tt, J = 10.5, 5.7 Hz, 1H), 1.44 – 1.01 (m, 6H), 0.84 (t, J = 7.1 Hz, 3H); C
NMR (126 MHz, C ) δ 208.72, 150.92, 92.06, 88.92, 77.77, 76.26, 35.70, 31.90, 25.23, 22.90,
4.18; IR (cm ) 1614.84, 1635.58, 1957.17, 2346.04, 2372.94, 2733.77, 2861.62, 2932.46,
6
D
6
-
1
1
3
1
+
+
024.40, 3046.73, 3119.21; HRMS (EI ) calc’d for [C11
H
18O] : m/z 166.13577, found
66.13540.
4

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Synthesis of 1-(vinyloxy)buta-2,3-dien-1-yl)cyclohexane (1e). 1-(vinyloxy)buta-2,3-dien-1-
yl)cyclohexane was prepared according to the same procedure used for the synthesis of allenyl
vinyl ethers. The crude mixture was purified by flash chromatography using an alumina column
1
and hexane as an eluent and afforded the allenyl vinyl ether in 65% yield as a colorless oil: ; H
NMR (500 MHz, C
6
D
6
) δ 6.37 (dd, J = 14.1, 6.0 Hz, 1H), 5.0 (ddd, J = 8.1, 6.8, 6.6 Hz, 1H),
4
6
0
0
2
2
1
.57 (δobs) (ABdd, JAB = 11 Hz, J = 6.8, 1.3 Hz, ∆υ = + 15.8 Hz, 1H; ABdd, JAB = 11 Hz, J =
.6, 1.4 Hz, ∆υ = - 15.8 Hz, 1H), 4.47 (dd, J = 14.1, 1.4 Hz, 1H), 4.06 (ddd, J = 8.1, 1.4, 1.3,
.75 Hz, 1H), 3.92 (dd, J = 7.9, 1.4 Hz, 1H), 1.94 – 1.80 (m, 1H), 1.74 – 1.44 (m, 5H), 1.19 –
1
3
.91 (m, 5H); C NMR (126 MHz, C
6
D
6
) δ 209.21, 151.30, 90.39, 88.81, 82.63, 75.72, 43.05,
-
1
8.83, 26.76, 26.24; IR (cm )1613.07, 1634.64, 1957.05, 2354.99, 2368.41, 2670.53, 2797.46,
+
+
858.10, 2944.86, 3023.59, 3118.15; HRMS (EI ) calc’d for [C12
H
18O] : m/z 178.13577, found
78.13610.
Synthesis of 5,5-dimethyl-4-(vinyloxy)octa-1,2,7-triene (1f). 5,5-dimethyl-4-(vinyloxy)octa-
1
,2,7-triene was prepared according to the same procedure used for the synthesis of allenyl vinyl
ethers. The crude mixture was purified by flash chromatography using alumina column and
1
hexane as an eluent and afforded the allenyl vinyl ether in 60% yield as a colorless oil: H NMR
(
500 MHz, C
dd, J = 16.6, 2.8 Hz, 1H), 4.98 (dd, J = 10.5, 2.8 Hz, 1H), 4.95 (ddd, J = 8.5, 6.66, 6.6 Hz, 1H),
.55 (δ ) (ABdd, J = 11 Hz, J = 6.66, 1.2 Hz, ∆υ = + 17.5 Hz, 1H; ABdd, JAB = 11 Hz, J =
6 6
D ) δ 6.33 (dd, J = 14.1, 6.6 Hz, 1H), 5.75 (ddt, J = 16.6, 10.5, 7.5 Hz, 1H), 5.01
(
4
6
3
1
8
obs
AB
.6, 1.3 Hz, ∆υ = - 15.8 Hz, 1H), 4.46 (dd, J = 14.1, 1.4 Hz, 1H), 4.05 (dd, J = 6.6, 1.4 Hz, 1H),
.91 (ddd, J = 8.6, 1.3, 1.1 Hz, 1H), 2.16 (dd, J = 13.5, 7.4 Hz, 1H), 1.99 (dd, J = 13.5, 7.4 Hz,
1
3
H), 0.93 (s, 3H), 0.85 (s, 3H); C NMR (126 MHz, C
6 6
D ) δ 209.75, 151.27, 134.89, 117.85,
-
1
8.98, 88.60, 84.45, 75.51, 43.56, 38.45, 22.96, 22.72; IR (cm )1614.41, 1636.51, 1957.44,
5

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+
2
345.85, 2366.55, 2876.89, 2933.43, 2965.27, 3005.78, 3077.76, 3119.69; HRMS (EI ) calc’d
+
for [C12H18O] : m/z 178.13577, found 178.13556.
Synthesis of (1-(vinyloxy)buta-2,3-dien-1-yl)cyclopropane (1g). (1-(vinyloxy)buta-2,3-
dien-1-yl)cyclopropane was prepared according to the same procedure used for the synthesis of
allenyl vinyl ethers. The crude mixture was purified by flash chromatography using an alumina
column and hexane as an eluent and afforded the allenyl vinyl ether in 55% yield as a colorless
1
oil: H NMR (500 MHz, C
6
D
6
) δ 6.33 (dd, J = 14.1, 6.6 Hz, 1H), 5.14 (ddd, J = 6.8, 6.4, 6.3 Hz,
1
H), 4.58 (δobs) (ABdd, JAB = 11 Hz, J = 6.4, 1.8 Hz, ∆υ = + 13.6 Hz, 1H; ABdd, JAB = 11 Hz, J
=
6.3, 1.6 Hz, ∆υ = - 13.6 Hz, 1H), 4.46 (dd, J = 14.1, 1.4 Hz, 1H) 4.47 (dd, J = 14.1, 1.4 Hz,
1
1
9
2
1
H), 4.05 (dd, J = 6.6, 1.4 Hz, 1H), 3.64 (dddd, J = 7.3, 6.8, 1.8, 1.6 Hz, 1H), 1.05 – 0.94 (m,
1
3
H), 0.41 – 0.24 (m, 3H), 0.23 – 0.13 (m, 1H); C NMR (126 MHz, C
6
D
6
) δ 208.82, 150.88,
-
1
1.31, 89.08, 81.18, 76.32, 16.10, 3.51, 2.14; IR (cm )1614.82, 1635.95, 2345.89, 2367.53,
+
+
888.82, 3010.67, 3084.60, 3118.1; HRMS (EI ) calc’d for [C
9
H
12O] : m/z136.08882, found
36.08901.
Synthesis of 4-(1-(vinyloxy)buta-2,3-dien-1-yl)benzonitrile (1h). 4-(1-(vinyloxy)buta-2,3-
dien-1-yl)benzonitrile was prepared according to the same procedure used for the synthesis of
allenyl vinyl ethers. The crude mixture was purified by flash chromatography using an alumina
column (10:1 Hexane : EtOAc) and the allenyl vinyl ether was obtained in 65% yield as a
1
colorless oil: H NMR (600 MHz, C
6
D
6
) δ 7.05 – 7.02 (m, 2H), 6.94 – 6.92 (m, 2H), 6.21 (dd, J
=
14.2, 6.7 Hz, 1H), 5.08 (d, J = 7.6, 1H), 4.96 (ddd, J = 7.6, 6.4, 6.3 Hz, 1H), 4.78 (δobs) (ABdd,
J
AB = 11.6 Hz, J = 6.3, 1.3 Hz, ∆υ = + 21.44 Hz, 1H; ABdd, JAB = 11.6 Hz, J = 6.2, 1.5 Hz, ∆υ=
1
3
-
21.44 Hz, 1H), 4.33 (dd, J = 14.2, 1.9 Hz, 1H), 4.03 (dd, J = 6.7, 1.9 Hz, 1H); C NMR (151
6 6
MHz, C D
) δ 208.88, 149.98, 145.12, 132.14, 126.98, 118.61, 112.19, 92.12, 90.51, 78.42,
-
1
7
7.48; IR (cm ) 1637.88, 1724.79, 1956.20, 2229.28, 2894.09, 2991.65, 3066.97, 3117.88;
+
+
HRMS (EI ) calc’d for [C13
H
11ON] : m/z 197.08407, found 197.08373.
6

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Synthesis of 1-fluoro-4-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1i). 1-fluoro-4-(1-
vinyloxy)buta-2,3-dien-1-yl)benzene was prepared according to the same procedure used for the
(
synthesis of allenyl vinyl ethers. The crude mixture was purified by flash chromatography using
an alumina column and hexane as an eluent and the allenyl vinyl ether was obtained in 71% yield
1
as a colorless oil: H NMR (500 MHz, CDCl
3
) δ 7.40 – 7.33 (m, 2H), 7.07 (ddd, J = 8.7, 5.8, 2.4
Hz, 2H), 6.44 (dd, J = 14.2, 6.7 Hz, 1H), 5.36 (ddd, J = 7.4, 6.5, 6.4 Hz, 2H), 5.29 (d, J =7.4 Hz,
H), 4.86 (δobs) (ABdd, JAB = 11.4 Hz, J = 6.5, 1.6 Hz, ∆υ = + 22.26 Hz, 1H; ABdd, JAB = 11.4
Hz, J = 6.5, 1.5 Hz, ∆υ = - 22.26 Hz, 1H), 4.39 (dd, J = 14.2, 1.9 Hz, 1H), 4.13 (dd, J = 6.7, 1.9
1
1
3
Hz, 1H); C NMR (126 MHz, CDCl
3
) δ 208.85, 161.54, 150.08, 136.18, 128.24, 115.41, 92.45,
-
1
9
3
0.33, 78.85, 77.55; IR (cm ) 1510.51, 1606.39, 1618.31, 1637.62, 1956.48, 2894.16, 3048,
+
+
118.28; HRMS (EI ) calc’d for [C12H11OF] : m/z 190.07940., found 190.07965.
Synthesis of 1-methyl-2-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1j). 1-methyl-2-(1-
vinyloxy)buta-2,3-dien-1-yl)benzene was prepared according to the same procedure used for the
(
synthesis of allenyl vinyl ethers. The crude mixture was purified by flash chromatography using
an alumina column and hexane as an eluent and afforded the allenyl vinyl ether in 60 % yield as
1
a colorless oil: H NMR (500 MHz, C
6
D
6
) δ 7.50 (dd, J = 7.7, 1.2 Hz, 1H), 7.12 – 7.00 (m, 2H),
6
.99 – 6.93 (m, 1H), 6.34 (dd, J = 14.3, 6.7 Hz, 1H), 5.41 (d, J = 7.4 Hz, 1H), 5.31 (ddd, J = 7.4,
.6, 6.5 Hz, 1H), 4.87 (δobs) (ABdd, JAB = 11.2 Hz, J = 6.6, 1.8 Hz, ∆υ = + 30 Hz, 2H; ABdd,
AB = 11.2 Hz, J = 6.5, 1.8 Hz, ∆υ = - 30 Hz, 1H), 4.03 (dd, J = 6.7, 1.7 Hz, 1H), 2.14 (s, 3H);
6
J
1
3
C NMR (151 MHz, CDCl
3
) δ 209, 150.6, 138.8, 135.3, 130.91,127.92, 126.54, 126.49, 92.11,
-
1
8
3
9.79, 77.07, 76.95, 19.02; IR (cm ) 1615.32, 1653.94, 1956.40,. 2929.25, 2955.59, 3026.13,
+
+
067.66, 3116.93; HRMS (EI ) calc’d for [C13
H
14O] : m/z 186.10447, found 186.10467.
7

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Synthesis of 1-ethyl-2-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1k). 1-ethyl-2-(1-
vinyloxy) buta-2,3-dien-1-yl)benzene was prepared according to the same procedure used for
(
the synthesis of allenyl vinyl ethers. The crude mixture was purified by flash chromatography
using an alumina column and hexane as an eluent and afforded the allenyl vinyl ether in 71 %
1
yield as a colorless oil: H NMR (500 MHz, CDCl
3
) δ 7.52 – 7.46 (m, 1H), 7.35 – 7.22 (m, 3H),
6
4
6
2
2
2
3
.45 (dd, J = 14.2, 6.7 Hz, 1H), 5.41 (d, J = 7.5 Hz, 1H), 5.31 (ddd, J = 7.5, 6.6, 6.6 Hz, 1H),
.87 (δobs) (ABdd, JAB = 11.2 Hz, J = 6.6, 1.65 Hz, ∆υ = + 30 Hz, 1H; ABdd, JAB = 11.2 Hz, J =
.6, 1.55 Hz, ∆υ = - 30 Hz, 1H), 4.39 (dd, J = 14.2, 1.7 Hz, 1H), 4.12 (dd, J = 6.7, 1.7 Hz, 1H),
1
3
.76 (qd, J = 7.6, 2.5 Hz, 2H), 1.29 (dd, J = 7.6, 7.6 Hz, 3H); C NMR (126 MHz, CDCl
3
) δ
08.78, 150.21, 141.22, 137.69, 128.80, 128.16, 126.49, 126.35, 92.29, 89.96, 77.25, 76.33,
-
1
5.39, 15.43; IR (cm ) 1615.33, 1726.11, 1956.35, 2876.3, 2934.98, 2968.81, 3024.77, 3066.05,
+
+
117.54; HRMS (EI ) calc’d for [C14H16O] : m/z 200.12012, found 200.12014.
Synthesis of 1-methyl-4-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1l). 1-methyl-4-(1-
vinyloxy)buta-2,3-dien-1-yl)benzene was prepared according to the same procedure used for the
(
synthesis of allenyl vinyl ethers. The crude mixture was purified by flash chromatography using
alumina column and hexane as an eluent and afforded the allenyl vinyl ether in 80% yield as a
1
colorless oil: H NMR (600 MHz, CDCl
3
) δ 7.30 (d, J = 7.3 Hz, 2H), 7.22 (d, J = 7.6 Hz, 2H),
6
.47 (dd, J = 14.1, 6.6 Hz, 1H), 5.41 (ddd, J = 7.6, 6.6, 6.6 Hz, 1H), 5.32 (d, J = 7.6 Hz, 1H), 4.9
(δobs) (ABdd, JAB = 11.2 Hz, J = 6.7, 6.5 Hz, ∆υ = 29 Hz, 2H ), 4.41 (dd, J = 14.2, 1.6 Hz, 1H),
1
3
4
1
3
.13 (dd, J = 6.6, 1.6 Hz, 1H), 2.39 (s, 3H); C NMR (151 MHz, CDCl ) δ 208.77, 150.25,
-
1
37.84, 137.46, 129.32, 126.48, 92.62, 90.02, 79.50, 77.26, 21.30; IR (cm ) 1514.26, 1617.45,
8

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry
This journal is © The Royal Society of Chemistry 2011
+
1
626.58, 1956.56, 3868.4, 2922.76, 3025.77, 2988.88, 3050.66, 3117.31; HRMS (EI ) calc’d for
+
13
[C H14O] : m/z 186.10447, found 186.10397.
Synthesis of 1,3-dimethyl-2-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1m). 1,3-dimethyl-2-
(1-(vinyloxy)buta-2,3-dien-1-yl)benzene was prepared according to the same procedure used for
the synthesis of allenyl vinyl ethers. The crude mixture was purified by flash chromatography
using an alumina column and hexane as an eluent and afforded the allenyl vinyl ether in 72%
1
yield as a colorless oil : H NMR (600 MHz, CDCl
3
) δ 7.10 (dd, J = 7.9, 7.1 Hz, 1H), 7.01 (d, J
=
7.5 Hz, 2H), 6.36 (dd, J = 15.0, 5.7 Hz, 1H), 5.78 (ddd, J = 6.6, 2.7, 2.5 Hz, 1H), 5.56 (ddd, J =
.6, 6.6, 6.6 Hz, 1H), 4.83 (δobs) (ABdd, JAB = 11.3 Hz, J = 6.5, 2.6 Hz, ∆υ = + 28.5 Hz, 1H;
ABdd, JAB = 11.3 Hz, J = 6.6, 2.6 Hz, ∆υ = - 28.5 Hz, 1H), 4.29 (dd, J = 14.1, 1.7 Hz, 1H), 4.01
6
1
3
(
3
dd, J = 6.6, 1.7 Hz, 1H), 2.42 (s, 6H), C NMR (151 MHz, CDCl ) δ 208.55, 149.95, 136.35,
-
1
1
2
2
35.91, 129.27, 127.82, 90.58, 89.42, 77.20, 76.33, 20.81; IR (cm ) 1614.78, 1956.28, 2345.78,
+
+
871.97, 2928.72, 2968.74, 3024.22, 3067.55, 3118.08; HRMS (EI ) calc’d for [C14
H
16O] : m/z
00.12012, found 200.12042.
Synthesis of 1,3,5-trimethyl-2-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene (1n). 1,3,5-
trimethyl-2-(1-(vinyloxy)buta-2,3-dien-1-yl)benzene was prepared according to the same
procedure used for the synthesis of allenyl vinyl ethers. The crude mixture was purified by flash
chromatography using an alumina column and hexane as an eluent and afforded the allenyl vinyl
1
ether in 70% yield as a colorless oil: H NMR (500 MHz, CDCl
3
) δ 6.84 (s, 2H), 6.35 (dd, J =
1
4
4.1, 6.6 Hz, 1H), 5.75 (ddd, , J = 6.7, 2.55, 2.55 Hz 1H), 5.54 (ddd, J = 6.7, 6.6, 6.6 Hz, 1H),
.82 (δobs) (ABdd, JAB = 11.2 Hz, J = 6.6, 2.55 Hz, ∆υ = + 24.8 Hz, 1H; ABdd, JAB = 11.2 Hz, J
6.6, 2.55 Hz, ∆υ = - 24.8 Hz, 1H), 4.28 (dd, J = 14.1, 1.6 Hz, 1H), 4.00 (dd, J = 6.6, 1.6 Hz,
=
1
3
1
H), 2.38 (s, 6H), 2.26 (s, 3H); C NMR (126 MHz, CDCl
3
) δ 208.52, 149.96, 137.38, 136.24,
9

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry
This journal is © The Royal Society of Chemistry 2011
-
1
1
1
32.97, 130.08, 90.73, 89.36, 77.16, 76.25, 20.99, 20.70; IR (cm ) 1578.39, 1612.71, 1634.96,
+
956.11, 2864.16, 2921, 2948.02, 2969.48, 3117.03, 3407.42; HRMS (EI ) calc’d for
+
[C
15
H
18O] : m/z 214.13577, found 214.13534.
Synthesis of 1-(4-methoxyphenyl)buta-2,3-dien-1-ol (1o). 1-(4-methoxyphenyl)buta-2,3-
dien-1-ol was prepared according to the same procedure used for the synthesis of allenyl vinyl
ethers The crude mixture was purified by flash chromatography using an alumina column (15:1
Hexane : EtOAc) as an eluent and afforded the allenyl vinyl ether in 65% yield as a colorless oil:
1
6 6
H NMR (500 MHz, C D ) δ 7.25 – 7.19 (m, 2H), 6.79 – 6.73 (m, 2H), 6.39 (dd, J = 14.1, 6.6
Hz, 1H), 5.39 (ddd, J = 7.4, 6.6, 1.8, 1.6 Hz, 1H), 5.21 (ddd, J = 7.4, 1.9, 1.8 Hz, 1H), 4.58 (δobs
)
(ABdd, JAB = 11 Hz, J = 6.6, 1.9 Hz, ∆υ = + 20.4 Hz, 1H; ABdd, JAB = 11 Hz, J = 6.5, 1.8 Hz,
∆
υ = - 20.4 Hz, 1H), 4.51 (dd, J = 14.2, 1.6 Hz, 1H), 4.07 (dd, J = 6.7, 1.6 Hz, 1H), 3.27 (s, 3H);
1
3
C NMR (126 MHz, C
6 6
D ) δ 208.79, 159.83, 150.61, 132.87, 128.11, 114.11, 93.31, 89.87,
-
1
7
2
2
9.40, 77.06, 54.72; IR (cm ) 1513.54, 1586.29, 1613.18, 1956.25, 2836.92, 2908.12, 2957.61,
+
+
935.63, 3001.14, 3037.71, 3116.36; HRMS (EI ) calc’d for [C13
H
14
O
2
] : m/z 202.09938, found
02.10044.
C. General Procedure for the gold (I)-Catalyzed Claisen Rearrangement of Allenyl Vinyl
Ethers
To a solution of AgSbF
0.01M). After stirring for 5 min at rt, the mixture was filtered through a cotton plug and added
to a mixture of the allenyl vinyl ether in CH Cl (0.05M). The reaction mixture was stirred at rt
until complete consumption of the starting material was observed by TLC. The reaction mixture
was then diluted with MeOH (2x CH Cl ) and NaBH (1 equiv.) was added. The resulting
6 2 2 2 2
in CH Cl (0.01M) was added a solution of IPrAuCl in CH Cl
(
2
2
2
2
4
mixture was stirred for 30 min, concentrated and the product was purified using column
chromatography.
1
0

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Synthesis of (E)-3-methylene-5-phenylpent-4-en-1-ol (2a). (E)-3-methylene-5-phenylpent-
-en-1-ol was prepared according to the general procedure for the gold-catalyzed Claisen
4
rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash chromatography
1
(5:1 Hexane:EtOAc) and afforded the alcohol in 86% yield as a white solid (m.p = 39
̊
NMR (500 MHz, C
6
D
6
) δ 7.31 – 7.25 (m, 2H), 7.22 – 7.05 (m, 3H), 6.76 (d, J = 16.3 Hz, 1H),
6
2
1
3
.58 (d, J = 16.3 Hz, 1H), 5.12 (s, 1H), 5.05 (s, 1H), 3.66 (t, J = 6.5 Hz, 2H), 2.48 (t, J = 6.5 Hz,
1
3
H); C NMR (126 MHz, C
6
D
6
) δ 143.05, 137.56, 130.95, 128.85, 128.83, 127.77, 126.87,
-
1
17.97, 61.32, 35.69; IR (cm ) 1602.95, 2345.91, 2368.8, 2883.25, 2947.87, 3026.55, 3081.97,
+
+
343.85; HRMS (EI ) calc’d for [C12H14O] : m/z 174.10447, found 174.10423.
Synthesis of (E)-5-(4-chlorophenyl)-3-methylenepent-4-en-1-ol (2b). (E)-5-(4-chloro phenyl)-
-methylenepent-4-en-1-ol was prepared according to the general procedure for the gold-
3
catalyzed Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash
chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 80% yield as a white solid
1
(m.p = 41
̊
3
) δ 7.41 – 7.25 (m, 4H), 6.78 (d, J = 16.3 Hz, 1H),
6
6
1
.55 (d, J = 16.3 Hz, 1H), 5.27 (s, 1H), 5.17 (s, 1H), 3.82 (td, J = 6.3, 5.8 Hz, 2H), 2.62 (t, J =
1
3
.5 Hz, 2H), 1.51 (t, J = 5.8 Hz, 1H); C NMR (126 MHz, CDCl
3
) δ 142.31, 135.67, 133.38,
-
1
31.10, 128.95, 127.77, 127.55, 118.89, 61.31, 35.45; IR (cm ) 1603.93, 2345.78, 2366.84, 28
1
1

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Synthesis of (E)-3-cyclohexylidene-5-phenylpent-4-en-1-ol (2c). (E)-3-cyclohexylidene-5-
phenylpent-4-en-1-ol was prepared according to the same procedure used for the gold-catalyzed
Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash
chromatography (5:1 Hexane:EtOAc) and afforded the propargylic alcohol in 65% yield as a
1
white solid (m.p = 39
̊
6
D
6
) δ 7.37 – 7.30 (m, 3H), 7.20 – 7.11 (m,
2
H), 7.10 – 7.02 (m, 1H), 6.67 (d, J = 16.1 Hz, 1H), 3.58 (t, J = 7.4 Hz, 2H), 2.65 (t, J = 7.4 Hz,
1
3
2
H), 2.31 (d, J = 6.0 Hz, 2H), 2.24 – 2.16 (m, 2H), 1.45 (m, 6H), 1.17 (s, 1H); C NMR (126
MHz, C6D6) δ 143.32, 138.93, 128.85, 127.44, 127.16, 126.60, 124.89, 62.04, 32.14, 31.90,
-
1
3
2
2
0.78, 28.93, 28.71, 27.13; IR (cm ) 1447.18, 1494.11, 1594.96, 1619.05, 2852.61, 2926.53,
+
+
969.02, 3022.30, 3045.51, 3078.32, 3335.03; HRMS (EI ) calc’d for [C17
H
22O] : m/z
42.16707, found 242.16668.
Synthesis of (E)-3-methylenehept-4-en-1-ol (2d). (E)-3-methylenehept-4-en-1-ol was
prepared according to the general procedure for the gold-catalyzed Claisen rearrangement for
allenyl vinyl ethers. The crude mixture was purified by flash chromatography (5:1
1
Hexane:EtOAc) and afforded the alcohol in 65% yield as a colorless oil: H NMR (500 MHz,
C
6
D
6
) δ 6.04 (d, J = 16.4 Hz, 1H), 5.62 (dt, J = 16.4, 7.0 Hz, 1H), 4.94 (d, J = 1.1 Hz, 1H), 4.86
(s, 1H), 3.57 (td, J = 6.7, 5.4 Hz, 2H), 2.35 (td, J = 6.7, 1.1 Hz, 2H), 1.97 (qd, J = 7.4, 1.3 Hz,
1
3
2
H), 1.34 – 1.16 (m, 6H), 1.03 (t, J = 5.4 Hz, 1H), 0.87 (t, J = 7.1 Hz, 3H); C NMR (126 MHz,
-
C
6 6
D ) δ 143.15, 132.25, 130.85, 115.09, 61.34, 36.08, 33.11, 31.74, 29.37, 22.87, 14.22; IR (cm
1
)
1606.80, 1956.31, 2345.72, 2366.08, 2857.01, 2873.64, 2927.84, 2957.85, 3013.16, 3081.85,
+
+
3
331.41; HRMS (EI ) calc’d for [C H O] : m/z 168.15142, found 168.15099.
11 20
1
2

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Synthesis of (E)-5-cyclohexyl-3-methylenepent-4-en-1-ol (2e). (E)-5-cyclohexyl-3-
methylene pent-4-en-1-ol was prepared according to the general procedure for the gold-catalyzed
Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash
1
chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 75% yield as a colorless oil: H
NMR (500 MHz, C
6
D
6
) δ 6.03 (d, J = 16.8 Hz, 1H), 5.61 (dd, J = 16.0, 7.1 Hz, 1H), 4.96 (d, J =
2
1
1
2
1
.0 Hz, 1H), 4.87 (d, J = 1 Hz, 1H), 3.58 (t, J = 6.7 Hz, 2H), 2.35 (td, J = 6.7, 1.0 Hz, 2H), 1.95 –
1
3
.82 (m, 1H), 1.71 – 1.54 (m, 5H), 1.26 – 0.96 (m, 5H); C NMR (126 MHz, C
6
D
6
) δ 143.30,
-
1
36.42, 129.81, 115.21, 61.36, 41.22, 36.04, 33.13, 26.41, 26.30; IR (cm ) 1605.78, 1647.3,
+
+
668.58, 2852.18, 2925.65, 3002.27, 3081.4, 3337.51; HRMS (EI ) calc’d for [C12
H
20O] : m/z
80.15142, found 180.15135.
Synthesis of (E)-6,6-dimethyl-3-methylenenona-4,8-dien-1-ol (2f). (E)-6,6-dimethyl-3-
methylenenona-4,8-dien-1-ol was prepared according to the general procedure for the gold-
catalyzed Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash
1
chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 60% yield as a colorless oil: H
NMR (500 MHz, C
6 6
D ) δ 6.01 (d, J = 16.2 Hz, 1H), 5.78 – 5.63 (m, 2H), 5.05 – 4.94 (m, 3H),
1
3
4
.90 (s, 1H), 3.61 (s, 2H), 2.46 – 2.36 (m, 2H), 1.99 – 1.93 (m, 2H), 0.94 (s, 6H); C NMR (126
MHz, C
6
D
6
) δ 143.13, 139.79, 135.60, 128.25, 117.15, 115.61, 61.40, 47.70, 36.08, 26.98; IR
-
1
+
(
cm ) 1606.26, 1639.73, 2345.71, 2365.92, 2961.87, 3004.25, 3078.41, 3345.14; HRMS (EI )
+
calc’d for [C12
H
20O] : m/z 180.15142, found 180.15143.
Synthesis of (E)-5-cyclopropyl-3-methylenepent-4-en-1-ol (2g). (E)-5-cyclopropyl-3-
methylenepent-4-en-1-ol was prepared according to the general procedure for the gold-catalyzed
1
3

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Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash
1
chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 77% yield as a colorless oil: H
NMR (500 MHz, C
6 6
D ) δ 6.13 (d, J = 15.7 Hz, 1H), 5.13 (dd, J = 15.7, 8.8 Hz, 1H), 4.92 (s,
1
H), 4.82 (d, J = 0.9 Hz, 1H), 3.55 (t, J = 6.7 Hz, 2H), 2.32 (td, J = 6.7, 0.9 Hz, 2H), 1.27 – 1.16
1
3
(
m, 1H), 0.57 – 0.48 (m, 2H), 0.28 – 0.21 (m, 2H); C NMR (126 MHz, C
6
D
6
) δ 142.88, 134.55,
-
1
1
2
29.95, 114.23, 61.22, 35.93, 14.56, 7.91, 7.37; IR (cm ) 1605.29, 1644.79, 2345.92, 2371.48,
+
+
9
883.32, 2947.7, 3006.7, 3082.94, 3357.67; HRMS (EI ) calc’d for [C H14O] : m/z 138.10447,
found 138.10417.
Synthesis of (E)-4-(5-hydroxy-3-methylenepent-1-en-1-yl)benzonitrile (2h). (E)-4-(5-
hydroxy-3-methylenepent-1-en-1-yl)benzonitrile was prepared according to the general
procedure for the gold-catalyzed Claisen rearrangement of allenyl vinyl ethers. The crude
mixture was purified by flash chromatography (2:1 Hexane:EtOAc) and afforded the alcohol in
1
9
–
3% yield as a white solid (m.p = 42
̊
6
D
6
) δ 7.04 – 6.95 (m, 2H), 6.74
6.69 (m, 2H), 6.48 (d, J = 16.2 Hz, 1H), 6.19 (d, J = 16.3 Hz, 1H), 5.08 (s, 1H), 5.00 (d, J = 0.9
1
3
Hz, 1H), 3.50 (t, J = 6.7 Hz, 2H), 2.31 (td, J = 6.7, 0.9 Hz, 2H), 0.95 (s,1H); C NMR (126
MHz, C ) δ 142.68, 141.26, 134.05, 132.24, 126.01, 126.83, 119.00, 118.98, 111.11, 61.19,
5.36; IR (cm ) 1603.82, 2226.22, 2345.89, 2367.79, 2941.66, 3397.56; HRMS (EI ) calc’d for
6
D
6
-
1
+
3
+
13
[C H13ON] : m/z 199.09972, found 199.09905.
Synthesis
of
(E)-5-(4-fluorophenyl)-3-methylenepent-4-en-1-ol
(2i).
(E)-5-(4-
fluorophenyl)-3-methylenepent-4-en-1-ol was prepared according to the general procedure for
the gold-catalyzed Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified
by flash chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 75% yield as a white
1
solid (m.p. = 42
̊
3
) δ 7.42 – 7.35 (m, 2H), 7.06 – 6.97 (m, 2H),
1
4

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry
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6
3
1
1
.73 (d, J = 16.3 Hz, 1H), 6.57 (d, J = 16.3 Hz, 1H), 5.26 (s, 1H), 5.15 (d, J = 1.0 Hz, 1H), 3.85 –
1
3
3
.78 (t, J = 6.5 Hz, 2H), 2.62 (td, J = 6.5, 1.0 Hz, 2H); C NMR (126 MHz, CDCl ) δ 142.34,
-
1
33.34, 130.28, 128.12, 127.61, 118.41, 115.82, 115.65, 61.30, 35.47; IR (cm ) 1508.59,
+
558.72, 1865.46, 2344.28, 2363.14, 2879.65, 2958.65, 3301.65; HRMS (EI ) calc’d for
+
[C
12
H
13OF] : m/z 192.09505, found 192.09496.
Synthesis of (E)-3-methylene-5-(o-tolyl)pent-4-en-1-ol (2j). (E)-3-methylene-5-(o-
tolyl)pent-4-en-1-ol was prepared according to the general procedure for the gold-catalyzed
Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash
1
chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 84% yield as a colorless oil: H
6 6
NMR (500 MHz, C D ) δ 7.41 (dd, J = 7.1, 1.9 Hz, 1H), 7.10 – 7.01 (m, 2H), 6.81 (d, J = 16.2
Hz, 1H), 6.63 (d, J = 15.7 Hz, 1H), 5.08 (s, 1H), 4.99 (d, J = 1.0 Hz, 1H), 3.62 (t, J = 6.7 Hz,
1
3
2
1
1
3
H), 2.45 (td, J = 6.7, 1.0 Hz, 2H), 2.13 (s, 3H), 1.38 (s, 1H); C NMR (126 MHz, C
6 6
D ) δ
43.44, 136.63, 135.85, 132.23, 130.58, 127.78, 126.72, 126.48, 125.74, 117.76, 61.37, 35.88,
-
1
9.70; IR (cm ) 1601.21, 1627.82, 2345.89, 2369.46, 2773.87, 2882.59, 2947.51, 3020.38,
+
+
056.53, 3346.93; HRMS (EI ) calc’d for [C13H16O] : m/z 188.12012, found 188.11968.
Synthesis of (E)-5-(2-ethylphenyl)-3-methylenepent-4-en-1-ol (2k). (E)-5-(2-ethylphenyl)-
3
-methylenepent-4-en-1-ol was prepared according to the general procedure for the gold-
catalyzed Claisen rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash
1
chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 79% yield as a colorless oil: H
NMR (500 MHz, C
6 6
D ) δ 7.46 – 7.41 (m, 1H), 7.11 – 7.01 (m, 3H), 6.91 (d, J = 16.1 Hz, 1H),
6
.66 (d, J = 16.1 Hz, 1H), 5.09 (s, 1H), 5.01 (d, J = 1.0 Hz, 1H), 3.64 (t, J = 6.5 Hz, 2H), 2.55 (q,
1
3
J = 7.6 Hz, 2H), 2.46 (t, J = 6.5 Hz, 2H), 1.59 (s, 1H), 1.11 (t, J = 7.6 Hz, 3H); C NMR (126
1
5

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry
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6 6
MHz, C D ) δ 143.39, 142.01, 135.88, 132.30, 129.02, 128.03, 126.51, 126.40, 126.03, 117.81,
-
1
6
2
1.37, 35.89, 26.73, 15.49; IR (cm ) 1601.01, 1794.25, 1809.59, 1918.68, 1945.30, 2345.93,
+
372.53, 2729.93, 2875.15, 2934.22, 2966.18, 3027.44, 3062.01, 3081.55, 3347.44; HRMS (EI )
+
calc’d for [C14
H
18O] : m/z 202.13577, found 202.13589.
Synthesis of (E)-3-methylene-5-(p-tolyl)pent-4-en-1-ol (2l). (E)-3-methylene-5-(p-tolyl)
pent-4-en-1-ol was prepared according to the general procedure for the gold-catalyzed Claisen
rearrangement for allenyl vinyl ethers. The crude mixture was purified by flash chromatography
1
(5:1 Hexane:EtOAc) and afforded the alcohol in 70% yield as a white solid (m.p = 41
̊
NMR (600 MHz, C
6
D
6
) δ 7.21 (d, J = 8.2 Hz, 2H), 6.97 (d, J = 7.9 Hz, 2H), 6.74 (d, J = 16.3 Hz,
1
6
1
2
3
H), 6.57 (d, J = 16.3 Hz, 1H), 5.08 (s, 1H), 4.99 (s, 1H), 3.60 (t, J = 6.7 Hz, 2H), 2.44 (td, J =
1
3
6 6
.7, 1.0 Hz, 2H), 2.12 (s, 3H), 1.32 (s, 1H); C NMR (151 MHz, C D ) δ 143.24, 137.44,
-
1
34.93, 130.06, 129.59, 128.92, 126.89, 117.33, 61.39, 35.85, 21.15; IR (cm ) 1512.38, 1601.8,
345.95, 2374.7, 2590.93, 2733.19, 2883.20, 2922.24, 2946.69, 3024.24, 3047.92, 3083.81,
+
+
359.95; HRMS (EI ) calc’d for [C13H16O] : m/z 188.12012, found 188.12032.
Synthesis of (E)-5-(2,6-dimethylphenyl)-3-methylenepent-4-en-1-ol (2m). (E)-5-(2,6-
dimethyl phenyl)-3-methylenepent-4-en-1-ol was prepared according to the general procedure
for the gold-catalyzed Claisen rearrangement of allenyl vinyl ethers. The crude mixture was
purified by flash chromatography (5:1 Hexane:EtOAc) and afforded the alcohol in 82% yield as
1
a white solid (m.p. = 42
̊
3
) δ 7.12 – 7.01 (m, 3H), 6.64 (d, J =
1
6.7 Hz, 1H), 6.31 (d, J = 16.7 Hz, 1H), 5.20 (s, 1H), 5.16 (d, J = 0.8 Hz, 1H), 3.89 (t, J = 6.5
1
3
3
Hz, 2H), 2.70 (td, J = 6.4, 0.8 Hz, 2H), 2.33 (s, 6H), 1.77 (s, 1H); C NMR (151 MHz, CDCl ) δ
-
1
1
42.58, 136.86, 136.06, 135.65, 127.91, 127.13, 126.79, 117.54, 61.30, 35.47, 21.07; IR (cm )
1
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+
1
605.48, 2345.96, 2370.39, 2734.37, 2948.56, 3019.26, 3064.46, 3361.28, HRMS (EI ) calc’d
+
for [C14H18O] : m/z 202.13577, found 202.13586.
Synthesis of (E)-5-mesityl-3-methylenepent-4-en-1-ol (2n). (E)-5-mesityl-3-methylenepent-
4
-en-1-ol was prepared according to the general procedure for the gold-catalyzed Claisen
rearrangement of allenyl vinyl ethers. The crude mixture was purified by flash chromatography
1
(
5:1 Hexane:EtOAc) and afforded the alcohol in 70% yield as a colorless oil: H NMR (500
MHz, CDCl
3
) δ 6.89 (s, 2H), 6.61 (d, J = 16.7 Hz, 1H), 6.28 (d, J = 16.7 Hz, 1H), 5.17 (s, 1H),
5
9
1
2
2
.13 (d, J = 0.9 Hz, 1H), 3.88 (td, J = 6.3, 5.9 Hz, 2H), 2.68 (td, J = 6.4, 0.9 Hz, 2H), 2.29 (s,
1
3
H), 1.63 (t, J = 5.9 Hz, 1H); C NMR (126 MHz, CDCl
3
) δ 142.66, 136.44, 136.04, 135.33,
-
1
33.91, 128.79, 127.17, 117.38, 61.32, 35.51, 21.07, 21.06; IR (cm ) 1604.44, 2342.99, 2361.06,
+
+
731.48, 2882.16, 2917.02, 2947.36; HRMS (EI ) calc’d for [C15
H
20O] : m/z 216.15142 found
16.15185.
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0