Gold(III) porphyrin-catalyzed cycloisomerization of allenones

Article abstract of DOI:10.1021/ol052696c

Gold(III) porphyrin-catalyzed cycloisomerization of allenones gave the corresponding furans in good to excellent yields (up to 98%) and with quantitative substrate conversions. By recovering the Au(III) catalyst, a recyclable catalytic system is developed with over 8300 product turnovers attained for the cycloisomerization of 1-phenyl-buta-2,3-dien-1-one. The versatility of the gold(III) porphyrin catalyst was exemplified by its application to the hydroamination and hydration of phenylacetylene in 73% and 87% yield, respectively.

Full text of DOI:10.1021/ol052696c

Supporting Information
for
Gold(III) Porphyrin-Catalyzed Cycloisomerization of
Allenones
Cong-Ying Zhou, Philip Wai Hong Chan and Chi-Ming Che*
Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of
Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong,
Pokfulam Road, Hong Kong
General Experimental Section: Reagents were obtained commercially and used without
further purification unless indicated otherwise. The gold(III) porphyrin catalysts and
S1, S2
allenone starting materials 1 were prepared following literature procedures.
Solvent
was removed under reduced pressure and the residue obtained was chromatographed on a
silica gel column (230-400 mesh) using a gradient solvent system (EtOAc: n-hexane as
1
13
eluant unless specified otherwise). H and C NMR spectra were measured on either a
Bruker DPX-400 or DPX-300 spectrometer. Chemical shifts (δ ppm) were determined
with tetramethylsilane (TMS) as internal reference. Mass spectra were determined on a
Finnigan MAT 95 mass spectrometer. IR spectra were recorded on Bio-RAD PTS-165
spectrometer.
General Procedure for Gold(III) Porphyrin-catalyzed Cycloisomerization of
Allenones 1 to Furans 2
To a acetone solution (3 mL) containing allenone 1 (0.5 mmol) was added gold(III)
porphyrin (5 µmol) and Brønsted acid (0.05 mmol) and the resultant mixture was stirred
o
at 60 C for 30 mins. The solvent was removed and the crude residue was purified by
silica gel column chromatography to give the furan product 2. The same procedure was
used for reactions with other Au(III) or Ag(I) catalysts.
S1

a
Table S1. Optimization of Reaction Conditions
Ph
O
catalyst
+
Ph
C
Ph
O
Ph
acid, solvent
O
2a
O
Me
3a
1
a
b, c
entry
acid
TFA
TFA
TFA
TFA
TFA
TFA
TFA
TFA
TFA
TFA
TsOH
catalyst
solvent
acetone
acetone
EtOH
time (h) yield (%)
d
e
1
2
3
4
5
6
7
8
[Au(TPP)]Cl
0.5
0.25
0.5
1
88
78
87
79
78
81
82
28
17
f
[Au(F20-TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]Cl
[Au(TPP)]OTf
1,2-dichloroethane
DMF
0.5
0.5
1
DMSO
3
CH CN
C
6
H
6
2
9
EtOAc
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
2
g
h
1
0
2
28
87
29
1
1
2
3
4
5
6
7
0.5
1
1
1
1
1
1
1
CH
3
CO
2
H
i
-
-
2
-
i
2
-
j
TFA
TFA
TFA
TFA
AuCl
AuPPh
[Au(salen)]Cl
AgNO
3
0.5
0.5
0.5
0.5
49
k
3
Cl
48
l
m
38
10
n
o
1
8
3
a
b1
c
Reactions were performed with 1 mol% catalyst at 60°C. H NMR yield. All substrate
1
d
conversions were quantitative based on H NMR analysis.
tetraphenylporphyrin.
tetrakis(pentafluorophenyl)porphyrin. Reaction conducted at room temperature. 31%
substrate conversion as determined by H NMR analysis. No reaction. The dimer 3a was
H
2
(TPP) = meso-
meso-
e
f
Isolated
yield.
H
2
(F20-TPP)
=
g
h
1
i
j
k
1
also isolated in 16% yield. 58% substrate conversion based on H NMR analysis.
l
m
2
H (salen) = N,N’-bis(salicylidene)ethylenediamine. 47% substrate conversion based on
1
n
o
H NMR analysis. Conducted with 2 mol% AgNO
3
catalyst. 21% substrate conversion
1
based on H NMR analysis. The dimer 3a was also isolated in 2% yield.
S2

S3
1
2
-Phenyl-furan 2a. Yield 88%; H NMR (300 MHz, CDCl
3
) δ 7.67 (d, 2H, J = 7.9
Hz), 7.46 (d, 1H, J = 1.8 Hz), 7.37 (t, 2H, J = 7.9 Hz), 7.22-7.27 (m, 1H), 6.64 (d, 1H, J =
1
3
3
1
.4 Hz), 6.46 (dd, 1H, J = 3.4, 1.8 Hz); C NMR (75 MHz, CDCl
3
) δ 153.9, 142.0,
+
30.9, 128.6, 127.3, 123.8, 111.6, 104.9; MS (EI) m/z 144 [M ]; HRMS (EI) calcd. for
C
10
H
8
O 144.0575, found 144.0572.
1
2
7
=
-p-Tolyl-furan 2b. Yield 84%; H NMR (300 MHz, CDCl
3
) δ 7.54 (d, 2H, J = 8.2 Hz),
.41 (d, 1H, J = 1.8 Hz), 7.14 (d, 2H, J = 8.2 Hz), 6.55 (d, 1H, J = 3.3Hz), 6.42 (dd, 1H, J
1
3
3.3, 1.8 Hz), 2.33 (s, 3H); C NMR (75 MHz, CDCl
3
) δ 154.2, 141.6, 137.1, 129.3,
−
1
1
1
1
28.2, 123.7, 111.5, 104.2, 21.2; IR (neat, cm ) 3292, 1633, 1435, 1340, 1287, 1131,

096, 1058, 642; MS (EI) m/z 158 [M ]; HRMS (EI) calcd. for C11
H10O 158.0731, found
58.0726.
S3
1
2
2
6
1
-(4-Methoxy-phenyl)-furan 2c. Yield 81%; H NMR (300 MHz, CDCl
3
) δ 7.59 (d,
H, J = 8.9Hz), 7.41 (d, 1H, J = 1.6 Hz), 6.90 (d, 2H, J = 8.9Hz), 6.50 (d, 1H, J = 3.3Hz),
1
3
.43 (dd, 1H, J = 3.3, 1.6 Hz), 3.81(s, 3H); C NMR (75 MHz, CDCl
3
) δ 158.9, 153.9,
+
41.3, 125.2, 123.9, 114.1, 114.5, 103.3, 55.2; MS (EI) m/z 174 [M ]; HRMS (EI) calcd.
for C11
H
10
O
2
174.0681, found 174.0685.
S4
1
2
3
-(4-Bromo-phenyl)-furan 2d. Yield 85%; H NMR (400 MHz, CDCl ) δ 7.45-7.51
13
(
m, 5H), 6.63 (d, 1H, J = 3.4Hz), 6.45 (dd, 1H, J = 3.4, 1.1 Hz); C NMR (100 MHz,

CDCl
3
) δ 152.8, 142.3, 131.8, 129.7, 125.3, 121.0, 111.8, 105.5; MS (EI) m/z 222 [M ];
7
HRMS (EI) calcd. for C10H BrO 221.9680, found 221.9679.
S3
1
2
7
1
-(3-Bromo-phenyl)-furan 2e. Yield 87%; H NMR (300 MHz, CDCl
3
) δ 7.81 (s, 1H),
.57 (d, 1H, J = 7.8 Hz), 7.46 (t, 1H, J = 0.9 Hz), 7.38 (dt, 1H, J = 7.8, 0.9 Hz), 7.23 (t,
1
3
3
H, J = 7.8Hz), 6.66 (d, 1H, J = 3.4Hz), 6.46-6.48 (m, 1H); C NMR (75 MHz, CDCl )
δ 152.8, 142.5, 132.7, 130.2, 130.1, 126.7, 122.8, 122.2, 111.8, 106.1; MS (EI) m/z 222
+
[
7
M ]; HRMS (EI) calcd. for C10H OBr 221.9680, found 221.9682.
S3

S5
1
2
-(2-Bromo-phenyl)-furan 2f. Yield 98%; H NMR (300 MHz, CDCl
3
) δ 7.78 (dd,
1H, J = 7.9, 1.6 Hz), 7.64 (dd, 1H, J = 7.9, 1.0 Hz), 7.51(dd, 1H, J = 1.8, 0.7 Hz), 7.35
1
3
(
dt, 1H, J = 7.4, 1.2 Hz), 7.08-7.17 (m, 2H), 6.51 (dd, 1H, J = 3.5, 1.8Hz); C NMR (75
MHz, CDCl ) δ 151.3, 112.2, 134.1, 131.2, 128.8, 128.3, 127.3, 119.6, 111.3, 110.5; MS
3
+
(
EI) m/z 222 [M ]; HRMS (EI) calcd. for C10
H
7
OBr 221.9680, found 221.9683.
S3
1
2
-(4-Chloro-phenyl)-furan 2g. Yield 86% ; H NMR (400 MHz, CDCl ) δ 7.57 (d,
3
2H, J = 8.7 Hz), 7.44 (d, 1H, J = 1.7 Hz), 7.34(d, 2H, J = 8.7 Hz), 6.61 (d, 1H, J = 3.4
1
3
Hz), 6.45 (dd, 1H, J = 3.4, 1.7Hz); C NMR (75 MHz, CDCl
3
) δ 152.9, 142.2, 132.9,
29.3, 128.8, 124.9, 111.7, 105.4; MS (EI) m/z 178 [M ]; HRMS (EI) calcd. for
OCl 178.0185, found 178.0187.
+
1
10 7
C H
S3
1
4
-Furan-2-yl-benzoic acid methyl ester 2h. Yield 92%; H NMR (300 MHz, CDCl
3
)
δ 8.03(d, 2H, J = 8.4Hz), 7.72(d, 2H, J = 8.4Hz), 7.51(d, 1H, J = 1.7Hz), 6.78(d, 1H, J =
1
3
3
.4Hz), 6.50(dd, 1H, J = 3.4, 1.7Hz), 3.92(s, 3H); C NMR (75 MHz, CDCl
3
) δ 166.7,
+
1
52.8, 143.0, 134.7, 129.9, 128.4, 123.3, 111.9, 107.1, 51.9; MS (EI) m/z 171 [M − Me];
HRMS (EI) calcd. for C H O 171.0446, found 171.0445.
11
7
2
S6
1
2
3
-(4-Nitro-phenyl)-furan 2i. Yield 91%; H NMR (300 MHz, CDCl ) δ 8.25 (d, 2H, J
=
8.9Hz), 7.79 (d, 2H, J = 8.9 Hz), 7.57 (d, 1H, J = 1.6 Hz), 6.88 (d, 1H, J = 3.4Hz), 6.55
1
3
(
dd, 1H, J = 3.4, 1.6Hz); C NMR (75 MHz, CDCl
3
) δ 151.6, 144.1, 136.4, 129.1, 124.3,
+
1
23.9, 112.4, 108.9; MS (EI) m/z 189 [M ]; HRMS (EI) calcd. for C H NO 189.0426,
1
0
7
3
found 189.0424.
S7
1
2
7
6
1
-Naphthalen-2-yl-furan 2j. Yield 80%; H NMR (400 MHz, CDCl ) δ 8.14 (s, 1H),
3
.75-7.86 (m, 4H), 7.52 (d, 1H, J = 1.7 Hz), 7.41-7.49 (m, 2H), 6.77 (d, 1H, J = 3.3Hz),
1
3
.52 (dd, 1H, J = 3.3, 1.7Hz); C NMR (75 MHz, CDCl
3
) δ 154.1, 142.3, 133.5, 132.6,
28.3, 128.2, 128.1, 127.7, 126.4, 125.9, 122.3, 122.1, 111.8, 105.7; MS (EI) m/z 194
+
[
M ]; HRMS (EI) calcd. for C14H10O 194.0732, found 194.0738.
S4

1
2
-(6-Bromo-naphthalen-2-yl)-furan 2k. Yield 85%; H NMR (300 MHz, CDCl
3
) δ 8.05
(
(
s, 1H), 7.93 (s, 1H), 7.67-7.76 (m, 3H), 7.50-7.53 (m, 2H), 6.75 (d, 1H, J = 3.3 Hz), 6.50
1
3
dd, 1H, J = 3.3, 1.7Hz); C NMR (75 MHz, CDCl ) δ 153.5, 142.5, 133.5, 131.9, 129.8,
3
−
1
1
29.77, 129.70, 128.5, 127.4, 123.8, 121.8, 119.7, 111.8, 105.9; IR (KBr, cm ) 3057,
+
1
699, 1470, 1429, 1215, 1161, 1007, 758; MS (EI) m/z 272 [M ]; HRMS (EI) calcd. for
OBr 271.9836, found 271.9835.
14 9
C H
1
6
-Furan-2-yl-naphthalene-2-carboxylic acid methyl ester 2l. Yield 88%; H NMR
300 MHz, CDCl ) δ 8.55 (s, 1H), 8.14 (s, 1H), 8.04 (d, 1H, J = 8.6Hz), 7.79-7.94 (m,
H), 7.54 (d, 1H, J = 1.6 Hz), 6.82 (d, 1H, J = 3.3 Hz), 6.53 (dd, 1H, J = 3.3, 1.6 Hz),
(
3
3
3
1
1
2
1
3
.97 (s, 3H); C NMR (75 MHz, CDCl ) δ 167.1, 153.5, 142.8, 135.7, 131.8, 130.8,
3
−
1
30.3, 129.7, 128.3, 127.2, 125.8, 123.0, 121.8, 111.9, 106.7, 52.2; IR (KBr, cm ) 3293,
+
707, 1425, 1286, 1057, 630; MS (EI) m/z 252 [M ]; HRMS (EI) calcd. for C H O
3
1
6
12
52.0786, found 252.0791.
1
2
-Anthracen-2-yl-furan 2m. Yield 84%; H NMR (300 MHz, CDCl
3
) δ 8.42 (s, 1H),
8
.36 (s, 1H), 8.29 (s, 1H), 7.97-8.00 (m, 3H), 7.74 (dd, 1H, J = 8.9, 1.6 Hz), 7.54 (d, 1H,
J = 1.2 Hz), 7.43-7.46 (m, 2H), 6.68 (d, 1H, J = 3.3Hz), 6.53 (dd, 1H, J = 3.3, 1.6 Hz);
1
3
C NMR (75 MHz, CDCl
3
) δ 154.4, 142.4, 132.2, 131.8, 131.6, 130.8, 128.6, 128.2,
−
1
1
3
28.1, 127.4, 126.5, 126.1, 125.5, 125.4, 122.3, 121.8, 111.8, 105.3; IR (KBr, cm )
+
025, 1686, 1443, 1356, 1201, 1007, 758, 690; MS (EI) m/z 244 [M ]; HRMS (EI) calcd.
for C H O 244.0888, found 244.0887.
1
8
12
1
1
,4-Difurylbenzene 2n. Yield 73%; H NMR (400 MHz, CDCl
3
) δ 7.68 (s, 4H), 7.47
(dd, 2H, J = 1.8, 0.7Hz), 6.66 (dd, 2H, J = 3.4, 0.7 Hz), 6.47 (dd, 2H, J = 3.4, 1.8 Hz);
1
3
−1
C NMR (100 MHz, CDCl
3
) δ 153.9, 142.1, 129.7, 124.0, 111.7, 105.1; IR (KBr, cm )
+
3
010, 1611, 1440, 1342, 1208, 1123, 1008, 769; MS (EI) m/z 210 [M ]; HRMS (EI)
calcd. for C14 210.0681, found 210.0681.
10 2
H O
S5

S8
1
[
3
2,2']Bifuranyl 2o. Yield 82%; H NMR (300 MHz, CDCl ) δ 7.40(d, 2H, J = 1.6 Hz),
1
3
6
1
1
3
.54 (d, 2H, J = 3.3 Hz), 6.44 (dd, 2H, J = 3.3, 1.6 Hz); C NMR (75 MHz, CDCl ) δ

41.7, 146.6, 111.3, 105.1; MS (EI) m/z 134 [M ]; HRMS (EI) calcd. for C
8
H
6
O
2
34.0367, found 134.0147.
S9
1
2
-Thiophen-2-yl-furan 2p. Yield 78%; H NMR (400 MHz, CDCl ) δ 7.40 (dd, 1H, J
3
=
1.8, 0.6 Hz), 7.25 (dd, 1H, J = 3.6, 1.1 Hz), 7.22 (dd, 1H, J = 5.1, 1.1 Hz), 7.03 (dd, 1H,
1
3
J = 5.1, 3.6Hz), 6.49 (d, 1H, J = 3.3Hz), 6.44 (dd, 1H, J = 3.3, 1.8Hz); C NMR (100
MHz, CDCl ) δ 149.5, 141.6, 133.8, 127.6, 124.1, 122.5, 111.6, 104.9; MS (EI) m/z 150
M ]; HRMS (EI) calcd. for C H OS 150.0139, found 150.0150.
3
+
[
8
6
S3
1
2
3
-Methyl-furan 2q. Yield 89%; H NMR (300 MHz, CDCl ) δ 7.27 (d, 1H, J = 1.7
1
3
Hz), 6.26 (dd, 1H, J = 2.9, 1.7 Hz), 5.96 (d, 1H, J = 2.9 Hz), 2.28 (s, 3H); C NMR (75

MHz, CDCl
3
) δ 152.1, 140.7, 110.2, 105.3, 13.3; MS (EI) m/z 82 [M ]; HRMS (EI)
calcd. for C H O 82.0419, found 82.0423.
5
6
S3
1
2
-Benzyl-furan 2r. Yield 92%; H NMR (400 MHz, CDCl
dd, 1H, J = 3.0, 1.9 Hz), 5.99 (d, 1H, J = 3.0Hz), 3.96 (s, 2H); C NMR (100 MHz,
CDCl ) δ 154.6, 141.4, 138.1, 128.7, 128.5, 126.4, 110.2, 106.2, 34.4; MS (EI) m/z 158
3
) δ 7.19-7.31 (m, 6H), 6.28
13
(
3
+
[
M ]; HRMS (EI) calcd. for C11
H10O 158.0731, found 158.0715.
S10
1
3
-Butyl-2-methyl-furan 2s. Yield 90%; H NMR (300 MHz, CDCl
3
) δ 7.20 (d, 1H, J
=
1.7 Hz), 6.18 (d, 1H, J = 1.7 Hz), 2.28-2.33 (m, 2H), 2.20 (s, 3H), 1.42-1.49 (m, 2H),
1
3
1
1
.26-1.36 (m, 2H), 0.91 (t, 3H, J = 7.3 Hz); C NMR (75 MHz, CDCl ) δ 147.0, 139.6,
3
+
18.9, 111.5, 32.6, 24.4, 22.3, 13.9, 11.4; MS (EI) m/z 138 [M ]; HRMS (EI) calcd. for
C H O 138.1044, found 138.1038.
9
14
1
2
2
=
3
-Methyl-5-pentyl-furan 2t. Yield 97%; H NMR (300 MHz, CDCl ) δ 5.83 (s, 2H),
.55 (t, 2H, J = 7.6 Hz), 2.24 (s, 3H), 1.57-1.64 (m, 2H), 1.24-1.35 (m, 4H), 0.90 (t, 3H, J
13
6.9Hz); C NMR (75 MHz, CDCl
3
) δ 154.8, 149.9, 105.6, 105.0, 31.4, 28.0, 27.8,
S6

−
1
2
2.4, 13.9, 13.4; IR (neat, cm ) 2958. 2932, 1715, 1470, 1377, 1101; MS (EI) m/z 152
+
[
M ]; HRMS (EI) calcd. for C10
H16O 152.1201, found 152.1209.
1
2
-Hexyl-5-styryl-furan 2u. Yield 95%; H NMR (300 MHz, CDCl
3
) δ 7.44 (d, 2H, J =
7
.5Hz), 7.31 (t, 2H, J = 7.3 Hz), 7.20 (t, 1H, J = 7.3 Hz), 6.95 (d, 1H, J = 6.2 Hz), 6.82
(d, 1H, J = 6.2 Hz), 6.23 (d, 1H, J = 3.1 Hz), 6.00 (d, 1H, J = 3.1 Hz), 2.64 (t, 2H, J = 7.6
1
3
Hz), 1.62-1.70 (m, 2H), 1.25-1.40 (m, 6H), 0.89 (t, 3H, J = 6.7 Hz)); C NMR (75 MHz,
CDCl ) δ 156.8, 151.5, 137.8, 128.6, 127.1, 126.1, 125.4, 116.7, 109.6, 106.8, 31.5, 28.8,
3
−
1
2
7
2
8.2, 27.9, 22.5, 14.0; IR (neat, cm ) 2929, 1598, 1530, 1494, 1447, 1017, 955, 778,
+
47, 691; MS (EI) m/z 254 [M ]; HRMS (EI) calcd. for C H O 254.16706, found
1
8
22
54.1669.
1
3
-Butyl-5-pentyl-2-styryl-furan 2v. Yield 90%; H NMR (300 MHz, CDCl
3
) δ 7.45 (d,
2H, J = 7.6 Hz), 7.32 (t, 2H, J = 7.3 Hz), 7.19 (t, 1H, J = 7.3 Hz), 6.90 (d, 1H, J = 6.2
Hz), 6.83 (d, 1H, J = 6.2 Hz), 5.91 (s, 1H), 2.62 (t, 2H, J = 7.5 Hz), 2.44 (t, 2H, J = 7.5
1
3
Hz), 1.62-1.71 (m, 2H), 1.50-1.60 (m, 2H), 1.28-1.46 (m, 6H), 0.87-0.97 (m, 6H); C
NMR (75 MHz, CDCl ) δ 156.0, 146.8, 137.9, 128.5, 126.8, 125.9, 125.3, 123.7, 114.8,
3
−
1
1
08.3, 32.5, 31.5, 30.1, 27.9, 24.8, 22.5, 22.3, 14.0, 13.8; IR (neat, cm ) 2934, 1599,
+
1
533, 1495, 1443, 1018, 945, 775, 684; MS (EI) m/z 296 [M ]; HRMS (EI) calcd. for
28O 296.2140, found 296.2132.
21
C H
1
3
-Butyl-2-methyl-5-pentyl-furan 2w. Yield 93%; H NMR (300 MHz, CDCl
3
) δ 5.76
(
s, 1H), 2.51 (t, 2H, J = 7.6Hz), 2.26 (t, 2H, J = 7.5 Hz), 2.15 (s, 3H), 1.54-1.65 (m, 2H),
1
3
1
.40-1.52 (m, 2H), 1.25-1.38 (m, 6H), 0.87-0.94 (m, 6H); C NMR (75 MHz, CDCl
3
) δ
153.5, 144.7, 119.4, 106.4, 32.6, 31.5, 28.0, 27.8, 24.5, 22.4, 22.3, 13.98, 13.90, 11.3; IR
−
1
+
(
(
neat, cm ) 2958, 2931, 1693, 1466, 1378, 1148, 929; MS (EI) m/z 208 [M ]; HRMS
EI) calcd. for C14 24O 208.1827, found 208.1819.
H
S7

Procedure for Recycling of [Au(TPP)]Cl for Allenone Cycloisomerization
To an acetone solution (30 mL) containing allenone 1a (15 mmol) was added
III
[
Au (TPP)]Cl (15 µmol) and CF
3
CO
2
H (1.5 mmol) and the resultant mixture was stirred
o
at 60 C for 2 h. About 27 mL of solvent was removed under reduced pressure and n-
hexane was added to the mixture to precipitate out the gold(III) porphyrin catalyst, which
was filtered and washed with n-hexane (3 x 40 mL). Excess solvent was removed under
1
reduced pressure and the product yield was determined by H NMR analysis. After each
reaction, the catalyst recovered by filtration was dried under reduced pressure. The
Cycloisomerization of allenone 1a was repeated a further nine times using the recovered
catalyst under the same reaction conditions.
Competitive Allenone Cycloisomerizations Catalyzed by [Au(TPP)]Cl
To a solution of 1a (0.5 mmol) and substituted phenyl allenone (0.5 mmol) in acetone (3
mL) was added [Au(TPP)]Cl (5 µmol) and TFA (0.05 mmol). The mixture was stirred at
o
1
5
0 C for 30 mins. The amount of substrate conversions were determined by H NMR
analysis.
+
Table S2. Variation of log k
X
/k
H
with σ for [Au(TPP)]Cl-catalyzed Cycloisomerization
6 4 2
of Para-substituted Allenones p-X-C H C(O)CH=C=CH 1a-d and 1g.
+
allenone
X
OMe
Me
H
k /k
log k /k
H(exptl)
σ
X
H
X
1
c
1.86
1.23
1
0.27
0.09
0
−0.78
−0.31
0
1b
1
1
a
g
Cl
0.89
0.85
−0.05
−0.07
0.11
0.15
1d
Br
S8

+
Figure S1. Linear Free-energy Correlation of log k
X
/k
H
vs. σ Plot for
Cycloisomerization of Para-substituted Allenones p-X-C
6
H
4
2
C(O)CH=C=CH 1a-d and
1
g Catalyzed by [Au(TPP)]Cl.
0.30
0.25
0.20
0.15
0.10
0.05
0.00
4-MeO
R = 0.998
+
ρ = −0.36
4
-Me
H
4
-Cl
-
-
0.05
0.10
4
-Br
-0.8
-0.6
-0.4
-0.2
0.0
0.2
+
σ
S11
Hydroamination of Phenylacetlyene Catalyzed by [Au(TPP)]Cl
Phenylacetlyene (0.5 mmol), p-anisidine (0.55 mmol) and [Au(TPP)]Cl (25 µmol) was
o
placed in a round bottom flask and stirred at 80 C for 12 h. On cooling the reaction
mixture to room temperature, (4-methoxyphenyl)(1-phenylethylidene)amine 5 was
obtained by re-crystallized by slowly diffusing n-hexane to a CH Cl solution containing
2
2
1
the reaction mixture. Yield 73%; H NMR (300 MHz, CDCl
3
) δ 7.97-8.00 (m, 2H), 7.42-
S9

7
.46 (m, 3H), 6.93 (d, 2H, J = 8.5 Hz), 6.78 (d, 2H, J = 8.5Hz), 3.80 (s, 3H), 2.27 (s, 3H);
1
3
C NMR (75 MHz, CDCl
3
) δ 165.4, 156.0, 152.0, 139.8, 130.3, 128.3, 127.1, 120.7,
+
1
14.3, 55.4, 17.3; MS (EI) m/z 225 [M ].
S12
Hydrolysis of Phenylacetlyene Catalyzed by [Au(TPP)]Cl
To a solution of phenylacetlyene (0.5 mmol) and water (2.5 mmol) in ethanol (3 mL) was
added [Au(TPP)]Cl (25 µmol) and H SO (0.05 mmol). The mixture was stirred at reflux
for 18 h. The reaction mixture was diluted with sat. NaHCO and extracted with Et O,
washed with brine, dried over MgSO . and filtered. Removel of the solvent under
2
4
3
2
4
eeduced pressure and purification of the resultant residue by flash chromatography gave
1
acetophenone 6. Yield 87%; H NMR (300 MHz, CDCl
3
) δ 7.96 (d, 2H, J = 7.3Hz), 7.56
13
(
3
t, 1H, J = 7.9 Hz), 7.46(t, 2H, J = 7.9 Hz), 2.61 (s, 3H); C NMR (75 MHz, CDCl ) δ
+
1
97.9, 137.1, 133.0, 128.5, 128.2, 26.5; MS (EI) m/z 120 [M ].
Deuterium Labeling Experiments
Gold(III) Porphyrin-catalyzed Cycloisomerization of 1r to 2r
To a solution of 1r (0.5 mmol) in (CD
3
)
2
CO (3 mL) and D
2
O (0.2 mL) was added
III
o
[
Au (TPP)]Cl (5 µmol) and CF CO D (0.1 mmol). The mixture was stirred at 60 C for
3
2
3
0 mins. The solvent was removed and the crude residue was purified by silica gel
column chromatography to 2r in 84% yield with complete substrate conversion and with
1
a deuterium content of 83% at C-3 as determined by H NMR analysis (Figure S1a).
1
Yield 84%; H NMR (400 MHz, CDCl
3
) δ 7.19-7.31 (m, 6H), 6.28 (dd, 0.17H, J = 3.0,
13
1
.9 Hz), 5.99 (s, 1H), 3.96 (s, 2H); C NMR (100 MHz, CDCl ) δ 154.6, 141.4, 138.1,
3
S10

−
1
1
1
1
28.7, 128.5, 126.5, 110.2, 106.1, 34.4; IR (neat, cm ) 3032, 2926, 1587, 1502, 1456,
+
155, 1070, 991, 939, 704; MS (EI) m/z 159 [M ]; HRMS (EI) calcd. for C11
H
9
DO
59.0793, found 159.0788.
3 2 3 2 2
Treatment of 1r with CF CO D in (CD ) CO and D O
3 2 2
To a solution of 1r (0.5 mmol) in in (CD ) CO (3 mL) and D O (0.2 mL) was added
o
CF CO D (0.1 mmol). The mixture was stirred at 60 C for 30 mins. The solvent was
3
2
1
removed. H NMR analysis of the crude residue revealed no deuterium exchange in 1r
was observed.
3 2 3 2 2
Treatment of 2r with [Au(TPP)]Cl and CF CO D in (CD ) CO and D O
3 2 2
To a solution of deuterium-free 2r (0.5 mmol) in (CD ) CO (3 mL) and D O (0.2 mL)
III
was added [Au (TPP)]Cl (5 µmol) and CF
3
CO
2
D (0.1 mmol). The mixture was stirred at
o
6
0 C for 30 mins. The solvent was removed and the remaining residue was purified by
1
silica gel column chromatography. H NMR analysis of 2r revealed no deuterium
exchange in the furan product was found, as shown in Figure S2.
S11

III
Figure S2. 1H NMR Spectra of (a) 2r obtained from [Au (TPP)]Cl-catalyzed
cycloisomerization of 1r in the presence of (CD
3
)
2
CO, D
2
O, and CF
3
CO
2
D, and (b)
O.
III
deuterium-free 2r treated with [Au (TPP)]Cl and CF
3
CO D in (CD
2
3
)
2
CO and D
2
(
a)
(
b)
S12

1
Figure S3. H NMR of 2-p-Tolyl-furan 2b.
S13

1
Figure S4. H NMR of 2-(6-Bromo-naphthalen-2-yl)-furan 2k.
S14

1
Figure S5. H NMR of 6-Furan-2-yl-naphthalene-2-carboxylic acid methyl ester 2l.
S15

1
Figure S6. H NMR of 2-Anthracen-2-yl-furan 2m.
S16

1
Figure S7. H NMR of 1,4-difurylbenzene 2n.
S17

1
Figure S8. H NMR of 2-Methyl-5-pentyl-furan 2t.
S18

1
Figure S9. H NMR of 2-Hexyl-5-styryl-furan 2u.
S19

1
Figure S10. H NMR of 3-Butyl-5-pentyl-2-styryl-furan 2v.
S20

1
Figure S11. H NMR of 3-Butyl-2-methyl-5-pentyl-furan 2w.
S21

References
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1
969.
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1
S10 Ma, S.; Li, L. Org. Lett. 2000, 2, 941.
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S22