Construction of nitrogen-containing 9-membered ring epoxy vinyl ethers via gold(I)-catalyzed intramolecular cyclization reactions of acyclic 5-aza-2,3-epoxy-7-yn-1-ols

Article abstract of DOI:10.1002/jccs.201400121

A series of substituted nitrogen-containing 9-membered epoxy vinyl ethers has been constructed from easily available 5-aza-2,3-epoxy-7-yn-1-ols. Attack of the hydroxyl group onto the gold(I)-activated alkyne gave the postulated 9-membered allylic vinyl ether gold intermediate which underwent protodeauration affording the 9-membered epoxy vinyl ethers.

Full text of DOI:10.1002/jccs.201400121

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Construction of Nitrogen-Containing 9-Membered Ring Epoxy Vinyl Ethers via
Gold(I)-Catalyzed Intramolecular Cyclization Reactions of Acyclic
5-Aza-2,3-epoxy-7-yn-1-ols
Hsin-Hui Lin, Yi-Ju Chen, Kuan-Yu Liao and Ming-Chang P. Yeh*
Department of Chemistry, National Taiwan Normal University, 88 Ding-Jou Road, Section 4, Taipei 116, Taiwan,
R. O. C.
(Received: Mar. 10, 2014; Accepted: May 2, 2014; Published Online: Jul. 25 2014; DOI: 10.1002/jccs.201400121)
A series of substituted nitrogen-containing 9-membered epoxy vinyl ethers has been constructed from
easily available 5-aza-2,3-epoxy-7-yn-1-ols. Attack of the hydroxyl group onto the gold(I)-activated
alkyne gave the postulated 9-membered allylic vinyl ether gold intermediate which underwent
protodeauration affording the 9-membered epoxy vinyl ethers.
Keywords: Alcohol; Alkyne; Claisen rearrangement; Epoxy; Gold; Vinyl ether.
INTRODUCTION
As part of our investigation into intramolecular cy-
ate 3. This failure may be attributed to the facile [3.3]-
sigmatropic rearrangement of the postulated reactive inter-
mediate 3 which led to pyrrolidines. In order to confirm the
key 9-endo-dig addition,10 we envisaged that the corre-
sponding 5-aza-2,3-epoxy-7-yn-1-ol 4 (Scheme III), gen-
erated from epoxidation of the known (Z)-5-aza-2-en-7-
yn-1-ols 12 with 1.2 molar equiv of m-chloroperbenzoic
acid (mCPBA), may be a good model to offer an evidence
in support of the 9-endo-dig addition hypothesis. Herein,
clization reactions of 2-en-7-yn-1-ols with various Lewis-
and Brønted acid, we reported a gold-catalyzed Claisen-
type rearrangement of cyclic 8-aryl-5-aza-2-en-7-yn-1-ols,
leading to azaspirocyclic ketones (Scheme I, eq 1).1 When
acyclic analogues, (Z)-8-aryl-5-azaoct-2-en-7-yn-1-ol 1,
was treated with a catalytic amount of the gold cationic spe-
cies, affording cis-3-aroyl-4-vinylpyrrolidine 2 (Scheme I,
eq 2).2 We have proposed an initial step involving an un-
usual 9-endo-dig attack of the hydroxyl group onto the
gold-activated alkyne (Scheme II). The resulting 9-mem-
bered allylic vinyl ether gold intermediate 3 underwent a
gold-assisted [3,3]-sigmatropic rearrangement to deliver
the 3,4-disubstituted pyrrolidine derivative 2. Although
several vinylgold(I) intermediates have been reported and
fully characterized in the literature,3-9 we are unable to ob-
tain the key 9-membered allylic vinyl ether gold intermedi-
APostulated reaction path for the formation
of cis-3-aroyl-4-vinylpyrrolidine (3) from
(Z)-8-aryl-5-azaoct-2-en-7-yn-1-ol (1)
Scheme II
Gold-catalyzed Claisen-type rearrange-
ments of nitrogen-containing 2-en-7-yn-1-
ols
Scheme I
* Corresponding author. Email: cheyeh@ntnu.edu.tw
Supporting information for this article is available on the www under http://dx.doi.org/10.1002/jccs.201400121
J. Chin. Chem. Soc. 2014, 61, 1281-1288
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1281

Article
Lin et al.
The labile 9-membered-ring vinyl ether ring may attribute
to the low isolation yield of 5a. NMR studies provided the
evidence for support of the structural assignments for 5a.
The 1H NMR spectrum of 5a showed two doublets centered
at d 7.77 and 7.38, respectively, and a broad multiplet,
ranged from d 7.33–7.26, assigned to seven aromatic pro-
tons; a triplet at d 5.27, assigned to the vinyl proton at C-6
(Figure 1); a doublet of doublets, centered at d 4.59, as-
signed to one of the two diastereotopic methylene protons
at C-3; a doublet of doublets, centered at d 4.29, assigned to
one of the two diastereotopic methylene protons at C-9; a
doublet at d 4.21, assigned to the two protons at C-7; a
multiplet, centered at d 3.29, assigned to the proton at C-2;
a doublet of doublets, centered at d 3.25, assigned to one of
the two diastereotopic methylene protons at C-3; a triplet of
doublets, centered at d 3.08, assigned to one of the two
diastereotopic methylene protons at C-1; a doublet of dou-
blets, centered at d 2.64, assigned to one of the two
diastereotopic methylene protons at C-9; and a singlet at d
2.48, assigned to the methyl protons at the tosyl group. The
13C NMR spectrum exhibited a signal at d 106.2 assigned to
the vinyl carbon at C-6.11
Synthesis of 5-aza-2,3-epoxy-7-yn-1-ols
Scheme III
4 from (Z)-5-azaoct-2-en-7-yn-1-ols 3
we describe a gold(I)-catalyzed intramolecular cyclization
reactions of 5-aza-2,3-epoxy-7-yn-1-ols leading to 9-mem-
bered epoxy vinyl ethers. In this transformation, attack of
the alcohol functionality onto the gold(I)-catalyzed alkyne
produced a 9-membered vinyl ether gold intermediate
which underwent protodeauration furnishing the 9-mem-
bered epoxy vinyl ether.
RESULTS AND DISCUSSION
To check the catalytic behavior of gold complexes in
the intramolecular addition reaction, we first carried out the
model reaction between 4a and AuCl3 (0.10 molar equiv)
in dichloromethane (DCM) at ambient temperature. How-
ever, only starting substrate 4a was recovered quantita-
tively after prolonged stirring for 24 h. Switching the cata-
lyst to NaAuCl4×2H2O resulted in decomposition of 4a. The
use of the two-component catalytic system [Ph3PAuCl/
AgSbF6] in DCM at ambient temperature for 24 h gave a
trace amount of cyclized product, identified as the 9-mem-
bered ring epoxy vinyl ether 5a (Figure 1). Changing the
co-catalyst system to 0.1 molar equiv of [Ph3PAuCl/
AgOTf] in DCM, 4a produced 5a in 25% isolated yield af-
ter the reaction was stirred at ambient temperature for 24 h.
Refluxing 5a with [Ph3PAuCl/AgOTf] (0.1 molar equiv) in
DCM for 3 h resulted in decomposition of 5a and gave a
mixture of unidentified compounds. The investigation of
various solvents in the presence of the [Ph3PAuCl/AgOTf]]
catalyst system revealed that THF, toluene and CH3CN
were ineffective. Thus, [Ph3PAuCl/AgOTf] (0.1 molar
equiv) in DCM at ambient temperature, albeit in low iso-
lated yield, was used as the standard reaction conditions.
With the optimized reaction conditions in hand, we
next examined the scope of the reaction using various aryl
and alkyl substituted alkynes with [Ph3PAuCl/AgOTf] in
DCM. The results of the gold-catalyzed cycloisomerization
reactions of 5-aza-2,3-epoxy-7-octyn-1-ols 4a–k to pro-
duce 9-membered epoxy vinyl ethers 5a–k are listed in Ta-
ble 1. In general, cyclization of substrates with various aryl
substituents at the terminal position of the acetylene, for
example 4a–h, afforded 9-membered epoxy vinyl ethers
5a–h in 16–30% yields (Table 1, entries 1-8). It seems that
the electronic effect of the substituent on the phenyl ring is
rather insensitive to the yield of the reaction. The low iso-
lated yields of 5a–h may be due to gradual decomposition
of the instable aryl vinyl ether functionality during aqueous
workup and purfication on silica-gel column chromatogra-
phy. Substrates 4i–k bearing an alkyl group (methyl, n-
butyl or allyl) at the alkyne terminus afforded higher yields
of the corresponding 9-membered epoxy vinyl ethers 5i–k
(50–69%, Table 1, entries 9-11) than those analogous bear-
ing an aryl substituent (4a–k). Structures of 5c (CCDC
970660), 5h (CCDC 970842), and 5k (CCDC 970662)
were confirmed by x-ray diffraction analysis.11 Figure 2
shows the ORTEP structure of 5c. The reaction path lead-
ing to 9-membered epoxy vinyl ethers 5 from 5-aza-2,3-
epoxyoct-7-yn-1-ol 4 was suggested in Scheme IV. Attack
Fig. 1. Structure of 5a.
1282
www.jccs.wiley-vch.de
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2014, 61, 1281-1288

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Synthesis of 9-Membered Ring Vinyl Ethers
Table 1. Synthesis of 9-membered epoxy vinyl ether 5
A plausible reaction path for the formation
Scheme IV
R
of 5
R
O
O
OH
10 mol % AuPPh3Cl/AgOTf
CH2Cl2, rt, 20-24 h
O
N
Ts
N
Ts
5
4
Entry
Substrate
R
Yield (%)[a]
1
4a
4b
4c
4d
4e
4f
phenyl
4-methylphenyl
naphthalen-1-yl
4-methoxyphenyl
4-bromophenyl
2-bromophenyl
3-carbethoxyphenyl
3-nitrophenyl
methyl
25 (5a)
22 (5b)
16 (5c)
20 (5d)
34 (5e)
16 (5f)
18 (5g)
30 (5h)
69 (5i)
50 (5j)
55 (5k)
2
3
4
5
6
7
4g
4h
4i
8
9
10
11
4j
n-butyl
4k
allyl
[a] Isolated yields after silica-gel column chromatography.
Scheme V Synthesis of compound 9
of the hydroxyl group onto the gold-activated alkyne gave
the postulated allylic vinyl ether gold intermediate 6, which
underwent proton migration to yield the gold-hydride 7.
The transient intermediate 7 provided the 9-membered ep-
oxy vinyl ether 5 after reductive elimination.
Interestingly, when substrate 8, bearing a diethylester
linkage at the tether, was subjected to a catalytic amount
(0.1 molar equiv) of [Ph3PAuCl/AgOTf] in DCM at ambi-
ent temperature for 6 h, delivering dioxabicyclo[3.2.1]oc-
tane derivative 9 in 68% isolated yield (Scheme V). Aplau-
sible reaction path for the formation of compound 9 from 8
is suggested in Scheme VI. Due to a Thorpe-Ingold effect
presenting by the germinal diester group,12-14 the oxirane
may be in close proximity of the alkyne moiety and at-
tacked at the gold-activated alkyne in a 6-exo-dig manner
A proposed reaction path for the formation
Scheme VI
of 9
Fig. 2. ORTEP drawing of 5c.
J. Chin. Chem. Soc. 2014, 61, 1281-1288
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
1283

Article
Lin et al.
followed by ring opening of the oxirane by the pendant
hydroxyl group in a concerted manner to furnish the vinyl
ether gold intermediate 10. Protodeauration of 10 led to the
formation of the epoxy vinyl ether 11. Protonation of the
vinyl ether gave 12. Addition of the oxirane at the cationic
carbonyl carbon center followed by a ring opening of the
oxirane with H2O afforded dioxabicyclic compound 9. It is
worth mentioning that three stereogenic centers of com-
pound 9 are created; however, only the single diastereomer
depicted was isolated. Rigorous proof of structure of 9
(CCDC 987755) is confirmed by X-ray diffraction analy-
sis.11
EXPERIMENTAL
General Considerations: All reactions were performed
with oven-dried glassware under nitrogen atmosphere unless oth-
erwise indicated. Anhydrous solvents or solutions were trans-
ferred via an oven-dried syringe. Tetrahydrofuran (THF), di-
chloromethane (DCM), acetonitrile and toluene was dried by
passing through a column of Al2O3. Flash column chromatogra-
phy was carried out with silica gel (230–400 mesh). Melting
points were determined in open capillaries and are uncorrected.
1H nuclear magnetic resonance (NMR) spectra were obtained
with 400 and 500 MHz spectrometers. The chemical shifts are re-
ported in parts per million with either Me4Si (0.00 ppm) or CDCl3
(7.26 ppm) as internal standard. 13C NMR spectra were recorded
with 100 and 125 MHz spectrometers with CDCl3 as the internal
standard. Infrared (IR) spectra were recorded as neat solutions.
Mass spectra were determined by using a spectrometer at an ion-
ization potential of 70 eV and were reported as mass/charge (m/e).
High-resolution mass spectra were obtained with a double-focus-
ing mass spectrometer.
Due to the fact that vinyl ether derivatives are labile
under acid conditions, 9-membered epoxy vinyl ether 5c
was subjected to a solution of 1.1 molar equiv of HOTf in
DCM at ambient temperature. The reaction occurred spon-
taneously and provided the dioxabicyclo[3.2.1]octane de-
rivative 13 as the only isomer isolated in 55% yield
(Scheme VII). Scheme VIII suggested a reaction path lead-
ing to 13. Protonation of 5c furnished intermediate 14. At-
tachment of HOTf to the oxirane via hydrogen bonding al-
lows the ring opening by HOTF from the bottom face fol-
lowed by attack of the hydroxyl group at the cationic car-
bonyl carbon center to provide 13.
General Procedure (I): Synthesis of 8-Aryl-5-aza-2,3-
epoxyoct-7-yn-1-ols (4a): To a stirring solution of cis-2-bu-
tene-1,4-diol (4.40 g, 50 mmol) in CH2Cl2 (50 mL) at 0 oC were
added Et3N (1.32 g, 13 mmol), TBSCl (1.506 g, 10 mmol) and
DMAP (0.124 g, 1 mmol). The reaction mixture was stirred at 30
oC for 3 h followed by quenching with 20 mL of water. The reac-
tion mixture was extracted with CH2Cl2 (20 mL × 3). The com-
bined extracts were washed with brine (5 mL × 1), dried over an-
hydrous MgSO4 (5 g), and concentrated under reduced pressure in
ice bath to give (Z)-4-((tert-butyldimethylsilyl)oxy)but-2-en-1-ol
as a crude oil. The crude product was used for the following step
without further purification. To a solution of triphenylphosphine
Scheme VII Formation of 13 from 5c
o
(3.93 g, 15 mmol) in 75 mL of THF under nitrogen at 0 C was
A Suggest path for the formation of 13
from 5c
Scheme VIII
added diisopropyl azodicarboxylate (DIAD, 3.00 g, 15 mmol).
The reaction was allowed to stir at 0 oC for 30 min followed by ad-
dition of N-tosylpropargylamine (2.09 g, 10 mmol). The mixture
o
was allowed to stir at 0 C for 30 min and to it was added (Z)-
4-((tert-butyldimethylsilyl)oxy)but-2-en-1-ol (2.03 g, 10 mmol).
The reaction was stirred at 0 oC for 30 min and at ambient temper-
ature for 2 h before being concentrated under reduced pressure to
give a crude oil. The oil was purified by flash column chromatog-
raphy (silica gel, ethyl acetate/hexanes 1:40) to produce (Z)-N-(4-
((tert-butyldimethylsilyl)oxy)but-2-en-1-yl)-4-methyl-N-(prop-
2-yn-1-yl)benzenesulfonamide (3.06 g, 7.77 mmol, 78%). In a
100-mL round-bottom flask equipped with a stirring bar were
added Pd(PPh3)4 (0.39 g, 0.3 mmol), CuI (0.11 g, 0.6 mmol) and
PhI (3.67 g, 18 mmol). The system was purged with N2 and added
Et3N (30 mL). The reaction was allowed to stir at ambient temper-
In conclusion, a gold-catalyzed synthesis of nitro-
gen-containing 9-membered epoxy vinyl ethers has been
developed. The reaction provides an evidence for a 9-
endo-dig cyclization the hydroxyl group onto the gold(I)-
activated alkyne. Further synthetic applications of the
9-membered epoxy vinyl ethers are currently underway in
our laboratory.
1284
www.jccs.wiley-vch.de
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2014, 61, 1281-1288

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Synthesis of 9-Membered Ring Vinyl Ethers
ature for 20 min followed by addition of (Z)-N-(4-((tert-butyl-
dimethylsilyl)oxy)but-2-en-1-yl)-4-methyl-N-(prop-2-yn-1-yl)-
benzenesulfonamide (5.90 g, 15.0 mmol). The reaction was left at
ambient temperature for 6 h. The reaction mixture was quenched
with saturated NH4Cl(aq). The mixture was extracted with CH2Cl2
(30 mL × 3). The CH2Cl2 solution was washed with brine, dried
over MgSO4, and concentrated under reduced pressure. The re-
sulting oil was purified by flash column chromatography on silica
gel, eluting with ethyl acetate/hexanes 1:20, to obtain (Z)-N-
(4-((tert-butyldimethylsilyl)oxy)but-2-en-1-yl)-4-methyl-N-(3-
phen-ylprop-2-yn-1-yl)benzenesulfonamide (6.09 g, 12.97 mmol,
86%). To a solution of the crude (Z)-N-(4-((tert-butyldimethyl-
silyl)oxy)but-2-en-1-yl)-4-methyl-N-(3-phen-ylprop-2-yn-1-yl)
benzenesulfonamide (6.00 g, 12.8 mmol) in THF (60 mL) was
added TBAF (4.01 g, 15.33 mol). The reaction was allowed to stir
at ambient temperature for 12 h. The mixture was concentrated
under reduced pressure and the residue was purified by flash col-
umn chromatography on silica gel, eluting with ethyl acetate/hex-
anes 1:2, to obtain (Z)-(3-(N-tosyl(3-phenylprop-2-yn-1-yl)ami-
no)methyl)prop-2-en-1-ol (2.14 g, 6.04 mmol, 47%). To a stirring
solution of (Z)-(3-(N-tosyl(3-phenylprop-2-yn-1-yl)amino)meth-
yl)prop-2-en-1-ol (2.21 g, 4.71 mmol) in CH2Cl2 (50 mL) at 0 oC
was added m-chloroperbenzoic acid (mCPBA, 1.22 g, 7.07
mmol). The reaction mixture was stirred at 0 oC for 2 h. The reac-
tion was then quenched with 20 mL of saturated K2CO3(aq). The
reaction mixture was extracted with CH2Cl2 (20 mL × 3). The
combined extracts were washed with brine (5 mL × 1), dried over
anhydrous MgSO4 (5 g), and concentrated to give a crude oil. The
oil was purified by flash column chromatography (silica gel, ethyl
acetate/hexanes 1:4) to produce 4a (0.86 g, 1.766 mmol, 37%).
((3-N-Tosyl-N-(3-phenylprop-2-yn-1-yl)amino)methyl)-
CuI (3.7 mg, 0.03 mmol), K2CO3 (0.41 g, 3.0 mmol), and 2 drops
of DBU in DMSO (3 mL) was stirred for 10 h. The mixture was
extraced with 0.1 M HCl(aq) (10 mL) and diethyl ether (3 × 10
mL). The combined extracts were dried over anhydrous MgSO4
(5 g), and concentrated to give a crude oil. The oil was purified by
flash column chromatography (silica gel, ethyl acetate/hexanes
1:10) to produce 4k (0.210 g, 0.62 mmol, 20%) as a yellow oil: 1H
NMR (400 MHz, CDCl3) d 7.73 (d, J = 8.0 Hz, 2H), 7.27 (d, J =
8.0 Hz, 2H), 5.63-5.53 (m, 1H), 5.07-4.98 (m, 2H), 4.26 (d, J =
18.2 Hz, 1H), 4.20 (d, J = 18.2 Hz, 1H), 3.79 (s, 2H), 3.48 (dd, J =
14.7, 5.6 Hz, 1H), 3.38 (dd, J = 14.7, 5.6 Hz, 1H), 3.43 (dd, J =
9.8, 5.5 Hz, 1H), 3.20 (dd, J = 9.5, 5.3 Hz, 1H), 2.71-2.70 (m, 3H),
2.40 (s, 3H); 13C NMR (100 MHz, CDCl3) d 143.7, 135.4, 131.6,
129.5, 127.5, 116.0, 83.1, 74.6, 59.8, 55.9, 54.8, 44.6, 38.2, 22.6,
21.3; IR (CH2Cl2) 3429, 2926, 2221, 1803, 1598, 1347, 1162,
1093, 1041 cm-1; MS (ESI) m/e 358.1 ([M + Na]+), 347.1, 281.3,
258.6; HRMS (ESI) calcd for C17H21NO4NaS [M + Na]+
358.1089, found 358.1080.
General Procedure (III): The Gold(I)-Catalyzed Cy-
clization of 5-Aza-2,3-epoxyoct-7-yn-1-ols 4: To an oven-dried
25 mL two-neck bottle equipped with a stirrer bar and capped
with a rubber septum was added AgOTf (8 mg, 0.03 mmol). The
apparatus was evacuated (oil pump) and filled with nitrogen three
times. To the reaction mixture were then added PPh3AuCl (15 mg,
0.03 mmol) and compound 4a (111 mg, 0.32 mmol) via syringe in
3 mL of CH2Cl2. The resulting mixture was stirred at ambient
temperature for 24 h. The resulting reaction mixture was filtered
through a bed of Celite. The filtrate was concentrated in vacuo to
give the crude mixture. The crude mixture obtained was purified
by flash column chromatography (silica gel, ethyl acetate/hex-
anes 1:8) to give 5a (30 mg, 0.081 mmol, 25%).
1
oxiran-2-yl)methanol (4a): A yellow oil: H NMR (400 MHz,
(Z)-4-Phenyl-7-tosyl-3,10-dioxa-7-azabicyclo[7.1.0]dec-
4-ene (5a): A white solid: mp 132-134 °C; 1H NMR (400 MHz,
CDCl3) d 7.77 (d, J = 6.5 Hz, 2H), 7.38 (d, J = 6.4 Hz, 2H), 7.33-
7.31 (m, 3H), 7.28-7.26 (m, 2H), 5.27 (t, J = 8.4 Hz, 1H), 4.59 (dd,
J = 11.6, 4.0 Hz, 1H), 4.29 (dd, J = 13.6, 2.8 Hz, 1H), 4.21 (d, J =
8.8 Hz, 2H), 3.29 (m, 1H), 3.25 (dd, J = 11.6, 7.4 Hz, 1H), 3.08
(dt, J = 10.8, 3.2 Hz, 1H), 2.64 (dd, J = 14.0, 10.8 Hz, 1H), 2.48 (s,
3H); 13C NMR (100 MHz, CDCl3) d 160.1, 143.7, 137.3, 134.2,
129.9, 129.2, 128.6, 127.1, 125.6, 106.2, 69.7, 53.2, 53.1, 43.2,
41.8, 21.5; IR (CH2Cl2) 3505, 2923, 1598, 1340, 1163 cm-1; MS
(ESI) m/e 394.1 ([M + Na]+), 380.2, 372.1, 317.2; HRMS (ESI)
calcd for C20H21NNaO4S [M + Na]+ 394.1084, found 394.1089.
(Z)-4-(p-Tolyl)-7-tosyl-3,10-dioxa-7-azabicyclo-[7.1.0]dec-4-
ene (5b): To a solution of AgOTf (12 mg, 0.048 mmol) and
PPh3AuCl (24 mg, 48 mmol) in 5.0 mL of CH2Cl2 at ambient tem-
perature for 21 h was added 4b (184 mg, 0.48 mmol). The reaction
CDCl3) d 7.77 (d, J = 8.2 Hz, 2H), 7.29-7.21 (m, 5H), 7.08 (d, J =
7.4 Hz, 2H), 4.50 (d, J = 18.5 Hz, 1H), 4.40 (d, J = 18.5 Hz, 1H),
3.79 (s, 2H), 3.58 (dd, J = 14.8, 5.6 Hz, 1H), 3.45 (d, J = 14.6, 5.7
Hz, 1H), 3.29 (dt, J = 9.8, 5.2 Hz, 1H), 3.21 (dt, J = 9.6, 5.0 Hz,
1H), 2.63 (m, 1H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3) d
143.9, 135.3, 131.4, 129.6, 128.5, 128.0, 127.6, 121.7, 85.9, 81.4,
59.8, 55.9, 54.9, 44.8, 38.7, 21.3; IR (CH2Cl2) 3520, 2923, 1594,
1347, 1159 cm-1; MS (ESI) m/e 372.1 ([M + Na]+), 354.1, 340.1,
312.1; HRMS (EI) calcd for C22H22NO4S [M + H]+ 372.1270,
found 372.1274.
Procedure (II): Synthesis of N-(Hex-5-en-2-yn-1-yl)-N-
((3-(hydroxyme-thyl)oxiran-2-yl)methyl)-4-methyl-benzene-
sulfonamide (4k): To a mixture of allyl bromide (0.54 g, 4.5
mmol), ((3-(N-tosyl-N-(prop-2-yn-1-yl)amino)methyl)oxiran-
2-yl)methanol (0.92 g, 3.0 mmol), Na2SO3 (0.16 g, 1.5 mmol),
J. Chin. Chem. Soc. 2014, 61, 1281-1288
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
1285

Article
Lin et al.
mixture was stirred for 24 h, and the crude mixture was purified
by flash column chromatography (silica gel, ethyl acetate/hex-
anes 1:8) to give 5b (37 mg, 0.096 mmol, 20%) as a colorless oil:
1H NMR (400 MHz, CDCl3) d 7.75 (d, J = 8.0 Hz, 2H), 7.35 (d, J
= 8.0 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H),
5.19 (t, J = 8.4 Hz, 1H), 4.56 (dd, J = 11.8, 4.2 Hz, 1H), 4.25 (dd, J
= 13.7, 2.2 Hz, 1H), 4.19 (d, J = 8.5 Hz, 2H), 3.29-3.18 (m, 2H),
3.06 (dt, J = 10.7, 3.1 Hz, 1H), 2.60 (dd, J = 13.4, 11.1 Hz, 1H),
2.47 (s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3) d 160.2,
143.7, 138.4, 137.4, 131.4, 130.0, 129.3, 127.1, 125.6, 105.4,
69.7, 53.2, 53.1, 43.2, 42.9, 21.5, 21.2; IR (CH2Cl2) 3025, 2925,
1645, 1598, 1454, 1351, 1162, 1090, 1052 cm-1; MS (ESI) m/e
408.1 ([M + Na]+), 374.3, 274.1, 242.3, 233.1, 172.1, 150.1;
HRMS (ESI) calcd for C21H23NO4NaS [M + Na]+ 408.1245,
found 408.1241. (Z)-4-(Naphthalen-1-yl)-7-tosyl-3,10-dioxa-
7-azab-icyclo[7.1.0]dec-4-ene (5c): To a solution of AgOTf (11
mg, 0.043 mmol) and PPh3AuCl (21 mg, 0.043 mmol) in 4.3 mL
of CH2Cl2 at ambient temperature was added 4c (194 mg, 0.43
mmol). The reaction mixture was stirred for 24 h, and the crude
mixture was purified by flash column chromatography (silica gel,
ethyl acetate/hexanes 1:15) to give 5c (66 mg, 0.147 mmol, 34%)
as a white solid: mp 86-87 °C; 1H NMR (400 MHz, CDCl3) d 8.08
(d, J= 7.8 Hz, 1H), 7.84 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 8.4 Hz,
2H), 7.51-7.44 (m, 2H), 7.40-7.35 (m, 3H), 7.27-7.25 (m, 1H),
5.31 (dd, J = 9.2, 7.4 Hz, 1H), 4.37 (dd, J = 14.1, 2.9 Hz, 1H), 4.29
(dd, J = 13.4, 3.4 Hz, 1H), 4.28-4.12 (m, 3H), 3.46 (dd, J = 12.8,
7.4 Hz, 1H), 3.27 (dd, J = 14.5, 3.4 Hz, 1H), 3.13-3.09 (m, 1H),
2.82 (dd, J = 14.1, 10.5 Hz, 1H), 2.47 (s, 3H); 13C NMR (100
MHz, CDCl3) d 159.9, 143.6, 137.1, 133.6, 132.1, 130.9, 130.0,
128.4, 127.7, 127.1, 126.8, 126.2, 125.2, 125.0, 111.8, 67.8, 54.1,
55.3, 46.1, 42.9, 21.5; IR (CH2Cl2) 3058, 2951, 1656, 1597, 1449,
1340, 1183, 1092 cm-1; MS (ESI) m/e 444.1 ([M + Na]+), 441.1,
374.1, 360.1, 319.1, 301.1; HRMS (ESI) calcd for C24H23NNaO4S
[M + Na]+ 444.1245, found 444.1240. Crystals suitable for X-ray
diffraction analysis were grown from CH2Cl2 and hexanes. (Z)-
4-(4-Methoxyphenyl)-7-tosyl-3,10-dioxa-7-azabicyc-lo[7.1.0]
dec-4-ene (5d): To a solution of AgOTf (41 mg, 0.16 mmol) and
PPh3AuCl (79 mg, 0.16 mmol) in 16.0 mL of CH2Cl2 at ambient
temperature was added 4d (682 mg, 1.6 mmol). The reaction mix-
ture was stirred for 24 h, and the crude mixture was purified by
flash column chromatography (silica gel, ethyl acetate/hexanes
1:15) to give 5d (108 mg, 0.26 mmol, 34%) as a white solid: mp
104-105 °C; 1H NMR (400 MHz, CDCl3) d 7.76 (d, J = 8.3 Hz,
2H), 7.36 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 2.0 Hz, 2H), 6.83 (d, J =
8.8 Hz, 2H), 5.13 (dd, J = 9.1, 7.9 Hz, 1H), 4.59 (dd, J = 7.4, 4.3
Hz, 1H), 4.27-4.19 (m, 2H), 3.82 (s, 3H), 3.31-3.19 (m, 1H), 3.06
(dt, J = 10.8, 3.3 Hz, 1H), 2.62 (dd, J = 13.8, 10.7 Hz, 1H), 2.48 (s,
3H); 13C NMR (100 MHz, CDCl3) d 160.4, 160.0, 143.6, 137.3,
129.9, 127.1, 127.0, 126.7, 114.0, 104.3, 69.6, 55.3, 53.2, 53.1,
43.1, 41.9, 21.5; IR (CH2Cl2) 3061, 2926, 1607, 1575, 1513,
1337, 1286, 1158, 1090 cm-1; MS (ESI) m/e 424.1 ([M + Na]+),
420.1, 291.6, 282.1, 177.1, 143.1, 121.1, 84.1; HRMS (ESI) calcd
for C21H23NNaO5S [M + Na]+ 424.1195, found 424.1196. (Z)-4-
(4-Bromophenyl)-7-tosyl-3,10-dioxa-7-azabicyclo[7.1.0]dec-
4-ene (5e): To a solution of AgOTf (24 mg, 0.048 mmol) and
PPh3AuCl (12 mg, 0.048 mmol) in 4.8 mL of CH2Cl2 at ambient
temperature was added 4e (184 mg, 0.48 mmol). The reaction
mixture was stirred for 24 h, and the crude mixture was purified
by flash column chromatography (silica gel, ethyl acetate/hex-
anes 1:15) to give 5e (41 mg, 0.11 mmol, 22%) as a colorless oil:
1H NMR (400 MHz, CDCl3) d 7.75 (d, J = 8.0 Hz, 2H), 7.35 (d, J =
8.0 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 5.19
(t, J = 8.4 Hz, 1H), 4.56 (dd, J = 11.8, 4.2 Hz, 1H), 4.25 (dd, J =
13.7, 2.2 Hz, 1H), 4.20 (s, 1H), 4.18 (d, J = 8.5 Hz, 1H), 3.29-3.18
(m, 2H), 3.06 (dt, J = 10.7, 3.1 Hz, 1H), 2.60 (dd, J = 13.4, 11.1
Hz, 1H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3) d 160.2,
143.7, 138.4, 137.4, 131.4, 130.0, 129.3, 127.1, 125.6, 105.4,
69.7, 53.2, 53.1, 43.2, 42.9, 21.5; IR (CH2Cl2) 3025, 2925, 1645,
1598, 1454, 1351, 1162, 1090, 1052 cm-1; MS (ESI) m/e 408.1
([M + Na]+), 374.3, 274.1, 242.3, 233.1, 172.1, 150.1: HRMS
(ESI) calcd for C21H23NNaO4S [M + Na]+ 408.1245, found
408.1241. (Z)-4-(2-Bromophenyl)-7-tosyl-3,10-dioxa-7-aza-
bicyclo[7.1.0]dec-4-ene (5f): To a solution of AgOTf (9 mg,
0.036 mmol) and PPh3AuCl (18 mg, 0.036 mmol) in 3.6 mL of
CH2Cl2 at ambient temperature was added 4f (164 mg, 0.36
mmol). The reaction mixture was stirred for 24 h, and the crude
mixture was purified by flash column chromatography (silica gel,
ethyl acetate/hexanes 1:15) to give 5f (27 mg, 0.06 mmol, 16%) as
a colorless oil: 1H NMR (400 MHz, CDCl3) d 7.74 (d, J = 8.2 Hz,
2H), 7.53 (d, J = 7.9 Hz, 1H), 7.33-7.15 (m, 5H), 5.19 (dd, J = 9.1,
7.6 Hz, 1H), 4.38 (dd, J = 14.1, 2.2 Hz, 1H), 4.25 (dd, J = 12.4, 4.9
Hz, 1H), 4.23-4.17 (m, 2H), 3.33 (dd, J = 12.4, 7.7 Hz, 1H), 3.21-
3.19 (m, 2H), 2.82 (dd, J = 14.2, 10.4 Hz, 1H), 2.44 (s, 3H); 13
C
NMR (100 MHz, CDCl3) d 157.9, 143.6, 137.2, 135.7, 133.6,
130.8, 130.3, 129.9, 127.4, 127.1,121.9, 112.2, 68.2, 53.8, 53.3,
44.6, 42.1, 21.5; IR (CH2Cl2) 3062, 2925, 1653, 1590, 1341,
1161, 1091, 1028 cm-1; MS (ESI) m/e 474.0, 472.0 ([M + Na]+),
470.0, 395.2, 315.6, 306.0; HRMS (ESI) calcd for C20H20NO4NaSBr
[M + Na]+ 472.0194, found 472.0185. Ethyl 3-(Z)-7-tosyl-
3,10-dioxa-7-azabicyclo[7.1.0]dec-4-en-4-yl)benzoate (5g): To
a solution of AgOTf (15 mg, 0.056 mmol) and PPh3AuCl (28 mg,
0.056 mmol) in 5.6 mL of CH2Cl2 at ambient temperature was
added 4g (250 mg, 0.56 mmol). The reaction mixture was stirred
for 24 h, and the crude mixture was purified by flash column chro-
1286
www.jccs.wiley-vch.de
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2014, 61, 1281-1288

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Synthesis of 9-Membered Ring Vinyl Ethers
matography (silica gel, ethyl acetate/hexanes 1:15) to give 5g (45
mg, 0.10 mmol, 18%) as a white solid: mp 164-165 °C; 1H NMR
(400 MHz, CDCl3) d 8.01-7.99 (m, 2H), 7.79 (d, J = 8.0 Hz, 2H),
7.47 (d, J = 7.8 Hz, 1H), 7.41-7.37 (m, 3H), 5.39 (t, J = 8.0 Hz,
1H), 4.62 (dd, J = 11.4, 3.7 Hz, 1H), 4.41 (q, J = 7.1 Hz, 2H), 4.30
(dd, J = 13.9, 2.6 Hz), 4.21 (d, J = 8.4 Hz, 2H), 3.28-3.22 (m, 2H),
3.05 (dt, J = 10.6, 3.6 Hz, 1H), 2.64 (dd, J = 13.7, 10.9 Hz, 1H),
2.47 (s, 3H), 1.41 (t, J = 7.1 Hz, 3H);13C NMR (100 MHz, CDCl3)
d 166.0, 159.2, 143.9, 137.2, 134.8, 131.2, 130.1, 130.0, 129.8,
128.7, 127.1, 126.7, 107.5, 69.8, 61.2, 53.1, 53.0, 43.3, 41.8, 21.5,
14.3; IR (CH2Cl2) 3055, 2924, 1719, 1454, 1353, 1287, 1162,
1089 cm-1; MS (ESI) m/e 466.1 ([M + Na]+), 463.3, 393.2, 360.3,
349.2, 242.3, 167.2; HRMS (ESI) calcd for C23H25NO6NaS [M +
Na]+ 466.1300, found 466.1294. (Z)-4-(3-Nitrophenyl)-7-tosyl-
3,10-dioxa-7-azabicyclo[7.1.0]dec-4-ene (5h): To a solution of
AgOTf (40 mg, 0.157 mmol) and PPh3AuCl (78 mg, 0.157 mmol)
in 15.7 mL of CH2Cl2 at ambient temperature was added 4h (655
mg, 1.57 mmol). The reaction mixture was stirred for 24 h, and
the crude mixture was purified by flash column chromatography
(silica gel, ethyl acetate/hexanes 1:15) to give 5h (196 mg, 0.47
21.4, 19.20; IR (CH2Cl2) 3025, 2948, 1677, 1338, 1187, 1158,
1097 cm-1; MS (ESI) m/e 332.1 ([M + Na]+), 328.1; HRMS (ESI)
calcd for C15H19NO4NaS [M + Na]+ 332.0932, found 332.0928.
(Z)-4-Butyl-7-tosyl-3,10-dioxa-7-azabicyclo[7.1.0]dec-4-ene
(5j): To a solution of AgOTf (7 mg, 0.026 mmol) and PPh3AuCl
(13 mg, 0.026 mmol) in 2.6 mL of CH2Cl2 at ambient temperature
was added 4j (88 mg, 0.26 mmol). The reaction mixture was
stirred for 24 h, and the crude mixture was purified by flash col-
umn chromatography (silica gel, ethyl acetate/hexanes 1:15) to
give 5j (49 mg, 0.13 mmol, 50%) as a colorless oil: 1H NMR (400
MHz, CDCl3) d 7.70 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.2 Hz, 2H),
4.55 (dd, J = 9.6, 7.5 Hz, 1H), 4.44 (dd, J = 10.2, 2.5 Hz, 1H), 4.21
(dd, J = 13.8, 3.1 Hz, 1H), 4.05-3.95 (m, 2H), 3.27-3.19 (m, 2H),
2.97 (dt, J = 10.7, 3.2 Hz, 1H), 2.59 (dd, J = 13.8, 10.7 Hz, 1H),
2.43 (s, 3H), 2.06-1.91 (m, 2H), 1.37-1.19 (m, 4H), 0.84 (t, J = 7.0
Hz, 3H); 13C NMR (100 MHz, CDCl3) d 163.3, 143.5, 137.3,
129.8, 127.0, 105.8, 68.5, 53.2, 53.0, 42.8, 41.5, 33.1, 28.4, 22.1,
21.5, 13.8; IR (CH2Cl2) 3062, 2956, 1672, 1598, 1467, 1343,
1162, 1094 cm-1; MS (ESI) m/e 374.1 ([M + Na]+), 371.1, 257.1;
HRMS (ESI) calcd for C18H25NO4NaS [M + Na]+ 374.1402,
found 374.1404. (Z)-4-Allyl-7-tosyl-3,10-dioxa-7-azabicyclo-
[7.1.0]dec-4-ene (5k): To a solution of AgOTf (15 mg, 0.059
mmol) and PPh3AuCl (29 mg, 0.059 mmol) in 5.9 mL of CH2Cl2
at ambient temperature was added 4k (197 mg, 0.59 mmol). The
reaction mixture was stirred for 24 h, and the crude mixture was
purified by flash column chromatography (silica gel, ethyl ace-
tate/hexanes 1:15) to give 5k (116 mg, 0.32 mmol, 55%) as a
white solid: mp 68-69 °C; 1H NMR (400 MHz, CDCl3) d 7.69 (d, J
= 8.3 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 5.66-5.59 (m, 1H), 5.07
(s, 1H), 5.04-5.02 (m, 1H), 4.60 (dd, J = 10.0, 7.0 Hz, 1H),
4.50-4.44 (m, 1H), 4.20 (dd, J = 13.8, 3.2 Hz, 1H), 4.05-3.94 (m,
2H), 3.28-3.22 (m, 2H), 2.98 (dt, J = 10.6, 3.2 Hz, 1H), 2.81-2.69
(m, 2H), 2.58 (dd, J = 13.9, 10.7 Hz, 1H), 2.43 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 161.6, 143.5, 137.2, 132.9, 129.9, 127.0,
117.9, 106.9, 68.9, 53.1, 53.0, 42.9, 41.4, 38.2, 21.5; IR (CH2Cl2)
3070, 2954, 1672, 1449, 1341, 1163, 914 cm-1; MS (ESI) m/e
358.1 ([M + Na]+), 355.1, 330.1, 319.2, 258.6, 249.1, 241.1;
HRMS (ESI) calcd for C17H21NO4NaS [M + Na]+ 358.1089,
found 358.1098. Crystals suitable for X-ray diffraction analysis
were grown from CH2Cl2 and hexanes. (1R,5S)-Dimethyl-5-
benzyl-7-(hydroxymethyl)-6,8-diox-abicyclo[3.2.1]octane-
3,3-dicarboxylate (9): To a solution of AgOTf (15 mg, 0.02
mmol) and PPh3AuCl (11 mg, 0.02 mmol) in 5.9 mL of CH2Cl2 at
ambient temperature was added 8 (80 mg, 0.22 mmol). The reac-
tion mixture was stirred for 12 h, and the crude mixture was fil-
tered through a bed of Celite and then purified by flash column
chromatography (silica gel, ethyl acetate/hexanes 1:5) to give 9
1
mmol, 30%) as a white solid: mp 169-170 °C; H NMR (400
MHz, CDCl3) d 8.43 (t, J = 1.8 Hz, 1H), 8.05-8.04 (m, 1H), 7.79
(d, J = 7.84 Hz, 1H), 7.74 (d, J = 8.2 Hz, 2H), 7.45 (t, J = 8.0 Hz,
1H), 7.32 (d, J = 8.1 Hz, 2H), 5.37 (dd, J =10.0, 7.2 Hz, 1H), 4.55
(dd, J = 13.2, 4.1 Hz, 1H) 4.34 (dd, J = 13.2, 8.1 Hz, 1H), 4.18 (d,
J = 14.7 Hz, 1H), 4.10 (dd, J = 14.1, 3.1 Hz, 1H), 3.84 (d, J = 14.8
Hz, 1H), 3.27-3.18 (m, 3H), 2.44 (s, 3H); 13C NMR (100 MHz,
CDCl3) d 157.9, 148.6, 144.3, 136.4, 135.8, 134.4, 130.0, 129.0,
127.3, 123.2, 121.4, 111.7, 65.39, 52.5, 52.4, 50.4, 46.9, 21.5; IR
(CH2Cl2) 3055, 2926, 1646, 1528, 1458, 1351, 1265, 1163, 1091
cm-1; MS (ESI) m/e 439.1 ([M + Na]+), 413.2, 393.3, 342.1, 289.6,
242.3, 220.0; HRMS (ESI) calcd for C20H20N2O6NaS [M + Na]+
439.0940, found 439.0944. Crystals suitable for X-ray diffraction
analysis were grown from CH2Cl2 and hexanes. (Z)-4-Methyl-
7-tosyl-3,10-dioxa-7-azabicyclo[7.1.0]dec-4-ene (5i): To a so-
lution of AgOTf (17 mg, 0.065 mmol) and PPh3AuCl (32 mg,
0.065 mmol) in 6.5 mL of CH2Cl2 at ambient temperature was
added 4i (200 mg, 0.65 mmol). The reaction mixture was stirred
for 24 h, and the crude mixture was purified by flash column chro-
matography (silica gel, ethyl acetate/hexanes 1:15) to give 5i (137
1
mg, 0.45 mmol, 69%) as a white solid: mp 78-79 °C; H NMR
(400 MHz, CDCl3) d 7.70 (d, J = 8.6 Hz, 2H), 7.30 (d, J = 8.1 Hz,
2H), 4.64 (t, J = 8.4 Hz, 1H), 4.52-4.44 (m, 1H), 4.19 (dd, J =
10.7, 2.9 Hz, 1H), 3.97 (d, J = 8.6 Hz, 2H), 3.30-3.22 (m, 2H),
2.98 (dt, J = 10.7, 2.9 Hz, 1H), 2.62 (dd, J = 14.0, 10.8 Hz, 1H),
2.43 (s, 3H), 1.74 (s, 3H); 13C NMR (100 MHz, CDCl3) d 159.42,
143.4, 137.2, 130.0, 126.8, 107.0, 68.0, 53.0, 52.9, 43.1, 41.6,
J. Chin. Chem. Soc. 2014, 61, 1281-1288
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
1287

Article
Lin et al.
(52 mg, 0.15 mmol, 68%) as a white solid: mp 97–99 °C; 1H NMR
(400 MHz, CDCl3) d 7.32–7.24 (m, 5H), 4.20 (dd, J = 4.8, 1.3 Hz,
1H), 4.10 (dd, J = 6.9, 4.6 Hz, 1H), 3.79 (s, 3H), 3.70 (s, 3H),
3.09–2.99 (m, 3H), 2.77 (ddd, J = 9.6, 5.5, 4.3 Hz, 1H), 2.72 (d, J
= 11.4 Hz, 1H), 2.60 (d, J = 10.4 Hz, 1H), 2.35 (d, J = 11.4 Hz,
1H), 2.12 (dd, J = 11.5, 3.4 Hz, 1H), 0.97 (dd, J = 6.1, 4.3 Hz, 1H);
13C NMR (100 MHz, CDCl3) d 171.6, 171.4, 134.9, 130.9, 127.9,
127.0, 106.5, 78.9, 74.2, 64.0,53.1, 51.5, 43.3, 39.6, 31.9; IR
(CH2Cl2) 3528, 2952, 1731, 1440, 1255 cm-1; HRMS (ESI) calcd
for C18H22O7Na [M + Na]+ 373.1263, found 373.1270. Crystals
suitable for X-ray diffraction analysis were grown from CH2Cl2
and hexanes. 7-(Naphthalen-1-yl)-4-tosyl-8,10-dioxa-4-azabi-
cyclo[5.2.1]decan-2-yl trifluoromethanesulfonate (13): To a
solution of 5c (0.089 g, 0.2 mmol) in 4.0 mL of CH2Cl2 at ambient
temperature was added TfOH (0.036 g, 0.24 mmol). The reaction
mixture was stirred for 12 h, and the crude mixture was purified
by flash column chromatography (silica gel, ethyl acetate/hex-
anes 1:10) to give 13 (65 mg, 0.11 mmol, 55%) as a white solid:
m.p. 131-132 °C; 1H NMR (400 MHz, CDCl3) d 8.37 (d, J = 8.1
Hz, 1H), 7.87-7.81 (m, 2H), 7.74 (d, J = 8.2 Hz, 3H), 7.67 (quin, J
= 7.5 Hz, 2H), 7.40 (t, J = 7.0 Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H),
5.55–5.50 (m, 1H), 4.66 (t, J = 4.6 Hz, 1H), 4.37 (d, J = 9.9 Hz,
1H), 3.97-3.84 (m, 3H), 3.41 (td, J = 12.6, 2.0 Hz, 1H), 3.30 (dd, J
= 14.5, 11.3 Hz, 1H), 2.76 (t, J = 12.0 Hz, 1H), 2.46 (s, 3H), 2.15
(d, J = 15.5 Hz, 1H); 13C NMR (100 MHz, CDCl3) d 143.8, 137.3,
135.9, 134.5, 129.9, 129.8, 129.7, 128.8, 127.0, 126.1, 125.9,
125.6, 124.8, 112.1, 82.6, 74.3, 64.8, 50.2, 48.2, 39.7, 21.5; IR
(CH2Cl2) 2946, 1598, 1417, 1346, 1211, 1160, 1091, 1020 cm-1;
MS (ESI) m/e 594.1 ([M + Na]+), 589.1, 572.1, 566.6, 553.3,
548.1, 529.1, 523.3, 523.3, 518.5, 498.4, 491.5; HRMS (ESI)
calcd for C25H24NO7NaS2F3 [M + Na]+ 594.0844, found
594.0845.
ACKNOWLEDGEMENTS
This work has been supported by Ministry of Science
and Technology (NSC 101-2113-M-003-002-MY3) and
National Taiwan Normal University.
REFERENCES
1. Yeh, M. C. P.; Pai, H. F.; Hsiow, C. Y.; Wang, Y. R. Organo-
metallics 2010, 29, 160.
2. Yeh, M. C. P.; Lin, M. N.; Chang W. J.; Liou, J. L.; Shih, Y. F.
J. Org. Chem. 2010, 75, 6031.
3. Akana, J. A.; Bhattacharyya, K. X.; Müller, P.; Sadighi, J. P.
J. Am. Chem. Soc. 2007, 129, 7736.
4. Bae, H. J.; Baskar, B.; An, S. E.; Cheong, J. Y.; Thangadurai,
D. T.; Hwang, I. C.; Rhee, Y. H. Angew. Chem. Int. Ed. 2008,
47, 2263-2266.
5. Hashmi, A. S. K.; Schuster, M.; Rominger, F. Angew. Chem.
Int. Ed. 2009, 48, 8247.
6. Zeng, X.; Kinjo, R.; Donnadieu, B.; Bertrand, G. Angew.
Chem. Int. Ed. 2010, 49, 942.
7. Chen, Y.; Wang, D.; Petersen, J. L.; Akhmedov, N. G.; Shi,
X. Chem. Commun. 2010, 46, 6147.
8. Hashmi, A. S. K.; Schuster, A. M.; Rominger, F. Adv. Synth.
Catal. 2010, 352, 971.
9. Zhu, Y.; Yu, B. Angew. Chem. Int. Ed. 2011, 50, 8329.
10. After our results published (ref. 2), a similar gold-catalyzed
enynols cyclization was also reported in the literature. Park,
Y.; Kim, S. Y.; Park, J. H.; Cho, J.; Kang, Y. K.; Chuang, Y.
K. Chem. Commun. 2011, 47, 5190.
11. The structure elucidationof the compoundwas accomplished
by X-ray diffraction analysis. CCDC 970660 (5c), CCDC
970842 (5h), CCDC 970662 (5k), and CCDC 987755 (9)
contain the supplementary crystallographic data for this pa-
per. These data can be obtained free of charge from The
Cambridge Crystallographic Data Center via www.ccdc.
cam.ac.uk/data_request/cif.
Supporting Information Available
12. Beesley, R. M.; Ingold, C. K.; Thorpe, J. F. J. Chem. Soc.
Trans. 1915, 107, 1080.
Data for compounds 4b-j and 8, NMR Spectra for
compounds 4a-k, 5a-k, 8, 9 and 13, and X-ray crystallo-
graphic information files for compounds 5c, 5h, 5k, and 9
are available.
13. Levine, M. N.; Raines, R. T. Chem. Sci. 2012, 3, 2412.
14. Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 8746.
1288
www.jccs.wiley-vch.de
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2014, 61, 1281-1288