Sequential Functionalization of the O-H and C(sp2)-O Bonds of Tropolones by Alkynes and N-Sulfonyl Azides

Article abstract of DOI:10.1002/adsc.201500829

Sequential copper-catalyzed [3+2] cycloaddition, rhodium-catalyzed O-H insertion, intramolecular 1,8-addition, and rearrangement starting from 1-alkynes, N-sulfonyl azides, and tropolones is demonstrated for the synthesis of the 2-functionalized aminotrop

Full text of DOI:10.1002/adsc.201500829

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DOI: 10.1002/adsc.201500829
Very Important Publication
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Sequential Functionalization of the O H and C(sp ) O Bonds of
Tropolones by Alkynes and N-Sulfonyl Azides
Boram Seo,a Woo Hyung Jeon,a Chul-Eui Kim,a Sanghyuck Kim,a
Sung Hong Kim,b and Phil Ho Leea,*
a
National Creative Research Initiative Center for Catalytic Organic Reactions, Department of Chemistry, Kangwon
National University, Chuncheon 200-701, Republic of Korea
E-mail: phlee@kangwon.ac.kr
Analysis Research Division Daegu Center, Korea Basic Science Institute, Daegu 702-701, Republic of Korea
b
Received: September 5, 2015; Published online: December 9, 2015
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500829.
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Abstract: Sequential copper-catalyzed [3+2] cyclo- bonds smoothly occurs in the C(sp ) O H bonds of
addition, rhodium-catalyzed O H insertion, intramo- tropolone
lecular 1,8-addition, and rearrangement starting from
À
1-alkynes, N-sulfonyl azides, and tropolones is dem-
onstrated for the synthesis of the 2-functionalized Keywords: 2-functionalized aminotropones; N-sulfo-
aminotropones in one pot. These results indicate that nyl-1,2,3-triazoles; rhodium catalysis; tandem reac-
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sequential functionalization of O H and C(sp ) O tion; tropolone
Introduction
in the presence of a Rh catalyst,[9] we envisioned that
if carbenoids would be employed in the reaction with
Tropones make up a significant class of seven-mem- tropolones bearing a 2-hydroxy group, novel function-
bered non-benzenoid aromatic compounds that can alized tropones would be produced due to the nucleo-
be subjected to higher order cycloaddition reactions[1] philic hydroxy group at the 2-position of tropolone as
to provide a large number of biologically active com- well as the electrophilic property of the tropone ring.
pounds[2] and natural products.[3] Aminotroponimines Herein we report the Rh-catalyzed reaction of tropo-
derived from tropolone having a 2-hydroxy group are lones with N-tosyl-1,2,3-triazoles for the synthesis of
also a typical group of ligands.[4] In this regard, intro- 2-functionalized aminotropones via sequential Rh-cat-
À
duction of new functional groups onto tropone and alyzed O H insertion, intramolecular 1,8-addition,
transformation of previously present functional and rearrangement in one pot [Eq. (2)]. A sequential
À
groups in the troponoid family are desirable. Al- Cu-catalyzed [3+2] cycloaddition, Rh-catalyzed O H
though there are several methodologies for the prepa-
ration of functionalized tropones in the literature, the
development of new and convenient methods to pre-
pare them is imperative.[5]
Lately, the synthetic utilization of N-sulfonyl-1,2,3-
triazoles as precursors of azavinyl Rh-carbenoids has
been explored.[6] For the first time, Murakami and co-
workers described that the Rh-catalyzed reaction of
N-sulfonyl-1,2,3-triazoles with tert-butyl alcohol effi-
ciently afforded the alkoxy enamines via carbenoid
À
insertion into the O H bond followed by imine-en-
amine tautomerization [Eq. (1), Scheme 1].[7] Fokin
and co-workers also reported the substrate scope of
[8]
À
the Rh-catalyzed O H insertion with alcohols. In
continuation of our studies directed toward azavinyl
Rh-carbenoid obtained from N-sulfonyl-1,2,3-triazole Scheme 1. Rh-catalyzed reactions of alcohols with triazoles.
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FULL PAPERS
Sequential Functionalization of the O H and C(sp ) O Bonds
insertion, intramolecular 1,8-addition, and rearrange-
ment sequence starting from 1-alkynes, N-sulfonyl
azides, and tropolones is also demonstrated for the
synthesis of the 2-functionalized aminotropones.
These results suggest that sequential functionalization
2
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of the O H and C(sp ) O bonds smoothly occurs in
2
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C(sp ) O H bonds at the 2-position of tropolones
[Eq. (3)].
Results and Discussion
First, we examined the Rh-catalyzed reaction of tro- Figure 1. X-ray structures of 3aa and (Z)-3aa’.
polone (1a) with N-tosyl-4-phenyl-1,2,3-triazole (2a)
derived from the Cu-catalyzed [3+2] cycloaddition of
phenylacetylene with N-tosyl azide (Table 1).[10] (0.2 mmol, 1 equiv.) using Rh2(OAc)4 (1.0 mol%) in
Chloroform and 1,4-dioxane in the presence of DCE (1.0 mL) at 808C for 1 h, affording 3aa in 95%
Rh2(OAc)4 (1.0 mol%) are totally ineffective (en- isolated yield via liberation of molecular nitrogen
tries 1 and 2). However, ethyl acetate gave 2-function- (entry 9). Rh2(esp)2 (1.0 mol%) and Rh2(OPiv)4
alized aminotropone 3aa in 30% yield. Next, a large (1.0 mol%) were less reactive, and 3aa was obtained
number of solvents such as cyclohexane, benzene, tol- in 23% and 37% yields, respectively, together with
uene, chlorobenzene, and 1,2-dichloroethane (DCE) (Z)-3aa’. The structures of 3aa and (Z)-3aa’ were con-
was screened to reveal that DCE was the solvent of firmed by X-ray crystallography (Figure 1).[11]
choice (entries 4–8). The optimal conditions were ob-
At the outset, 4-phenyltriazoles 2 possessing
tained from a reaction of 1a (1.2 equiv.) with 2a a broad variety of sulfonyl groups at N-1 were exam-
ined in the reaction with tropolone (1a) (Scheme 2).
The wide range of sulfonyl groups of triazoles 2 did
Table 1. Reaction optimization.[a]
not largely influence the reaction efficiency. When
tropolone 1a was treated with 4-methoxyphenyl-sub-
stituted triazole 2b, the Rh-catalyzed reaction took
place to give rise to tropone 3ab in 85% yield. N-4-
Trifluoromethylbenzenesulfonyltriazole 2c is slightly
less reactive. Methane- and 2-methylethanesulfonyl-
triazoles were smoothly converted to the correspond-
ing tropones 3ad (88%) and 3ae (75%).
Entry
Solvent
T [oC]
t [h]
Yield[%][b]
1
2
3
4
5
6
7
8
CHCl3
1,4-dioxane
EtOAc
cyclohexane
benzene
toluene
chlorobenzene
DCE
60
80
80
80
80
80
80
80
80
100
100
6
6
6
6
4
6
4
4
1
6
5
0
0
30
56
95
72
83
96
9[c]
10[e]
11[f]
DCE
DCE
DCE
98 (95)[d]
23 (21)[g]
37 (23)[g]
[a]
Reactions were carried out with 1a (0.24 mmol), 2a
(0.2 mmol), and Rh2(OAc)4 (1.0 mol%) in solvent
(2.0 mL) under an N2 atmosphere.
NMR yield using CH2Br2 as an internal standard.
DCE (1.0 mL) was used.
Isolated yield of 3aa.
Rh2(esp)2 (1.0 mol%) was used.
Rh2(OPiv)4 (1.0 mol%) was used.
Isolated yield of (Z)-3aa’.
[b]
[c]
[d]
[e]
[f]
Scheme 2. Synthesis of 2-functionalized aminotropones
using N-sulfonyl-1,2,3-triazoles and tropolone.
[g]
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Boram Seo et al.
pones in excellent yields. However, electron-with-
drawing 4-fluoro- and 2-bromophenyl-substituted tri-
azoles (2j and 2l) were less reactive, and tropones
(3aj and 3al) were produced in 68% and 48% yields,
respectively. In contrast, 3-chloro- and 4-bromophen-
yl-substituted triazoles (2k and 2m) provided the 2-
functionalized aminotropones in good yields. Triazole
2n having a 4-trifluoromethylphenyl substituent was
transformed to the desired product 3an. Acetyl and
methoxycarbonyl groups are suitable for the Rh-cata-
lyzed reaction at the 2-position of tropolone, furnish-
ing the desired products 3ao and 3ap in good yields.
When 2-naphthyl-substituted triazole (2q) was reacted
with tropolone 1a, the Rh-catalyzed reaction took
À
place via sequential functionalization of O H and
C(sp ) O bonds to deliver 3aq in 89% yield. Thio-
2
À
phen-3-yl-substituted triazole (2r) underwent the Rh-
catalyzed reaction to produce 3ar in 55% yield. The
Rh-catalyzed reaction was amenable to 4-n-butyl- and
benzyl-substituted triazoles to give 3as and 3at in
72% and 65% yields, respectively. 4-Cyclohexenyltri-
azole 2u was compatible with the present method,
producing the desired 3au in 82% yield.
Stimulated by these results, we next examined the
scope and limitation of the Rh-catalyzed reaction by
Scheme 3. Synthesis of 2-functionalized aminotropones
using N-tosyl-1,2,3,-triazoles and tropolone.
To investigate the scope and functional group toler-
ance of this transformation, we investigated a variety
of substituents on the aryl ring of N-tosyl-4-aryl-1,2,3-
triazoles 2 under the optimal reaction conditions
(Scheme 3). Electronic variation of substituents on
the aryl ring of 2 slightly effected the reaction effi-
ciency. For instance, 4-aryl-1,2,3-triazoles having elec-
tron-donating 3- and 4-methyl and 2- and 4-methoxy
groups were subjected to the Rh-catalyzed reaction
À
via sequential Rh-catalyzed O H insertion, intramo-
lecular 1,8-addition, and rearrangement in one pot, af-
Scheme 4. Synthesis of 2-functionalized aminotropones
fording the corresponding 2-functionalized aminotro- using N-tosyl-1,2,3-triazoles and 5-substituted tropolones.
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Sequential Functionalization of the O H and C(sp ) O Bonds
the synthesis of tropone (3aa) through a three-compo-
nent reaction in one pot. N-Tosyl azide 4 and phenyl-
acetylene in the presence of copper(I) thiophene-2-
carboxylate (CuTC, 10.0 mol%) in DCE were placed
in a flask and the mixture was stirred at 508C. After
disappearance of the two starting materials on TLC
after 1h, tropolone 1a was added to the reaction mix-
ture, and the mixture was stirred at 808C for 3 h, af-
fording 3aa in 70% yield. The three-component reac-
tion in one pot was compatible with phenylacetylenes
bearing 3- and 4-methyl and 3-chloro substituents on
the phenyl ring, providing a large number of 2-func-
tionalized aminotropones (3af, 3ag, and 3ak) in mod-
erate to good yields ranging from 51% and 64%.
When (Z)-3aa’ was heated in dichloroethane at
808C for 1 h, the product 3aa was produced in 92%
yield via intramolecular 1,8-addition followed by rear-
rangement [Eq. (4)]. This result indicates that (Z)-
3aa’ is involved as an intermediate in the Rh-cata-
lyzed reaction of tropolone.
Scheme 5. Synthesis of 2-functionalized aminotropones from
N-tosyl azide, 1-alkynes, and tropolone in one pot.
variation of tropolones 1 and N-tosyl-4-aryl-1,2,3-tri-
azoles 2 (Scheme 4). 5-Phenyltropolone smoothly un-
derwent the reaction with 4-phenyl- and 4-(4-meth-
oxy)phenyltriazoles, producing the corresponding tro-
pones 3ba and 3bi in good yields. 5-Bromotropolone
took part in the Rh-catalyzed reaction to provide the
desired 2-functionalized aminotropones (3ca, 3ci, and
3ck) in good to excellent yields ranging from 66% to
With these results in hand, a feasible mechanism
95%. 5-(4-Fluorophenyl)tropolone also worked, lead- for the Rh-catalyzed reaction from N-tosyl azide, 1-al-
ing to the desired tropone 3di in 83% yield. When 5- kynes, and tropolones is depicted in Scheme 6. First,
(4-methoxyphenyl)tropolone was subjected to the Rh- a reversible ring-chain tautomerization of N-sulfonyl-
catalyzed reaction under the optimal conditions, the triazoles 2 derived from Cu-catalyzed [3+2] cycload-
corresponding tropone 3ei was produced in 68% dition of 1-alkynes with N-sulfonyl azides provides
yield.
azavinyl carbene A. The following irreversible reac-
Next, we tried to synthesize 2-functionalized amino- tion of A with Rh catalyst delivers azavinyl Rh-carbe-
tropones from N-tosyl azide, 1-alkynes, and tropolone noid B with evolution of molecular nitrogen. Nucleo-
in one pot to demonstrate the synthetic efficiency of philic attack of the hydroxy group of tropolone 1 to
the Rh-catalyzed reaction (Scheme 5). We attempted the electrophilic azavinyl Rh-carbenoid B affords Rh-
Scheme 6. A proposed mechanism.
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Boram Seo et al.
bound zwitterionic intermediate C. Proton transfer Preparation of Starting Materials
with regeneration of the Rh catalyst yields (Z)-3aa’.
The tropolone 1a was purchased and was used as received.
Tropolone substrates 1b, 1c, 1d, and 1e were prepared ac-
cording to reported procedures.[12,13] The analytical data of
compounds 1b[12] and 1c[14] have already been reported.
5-(4-Fluorophenyl)tropolone (1d): Green solid; mp 132–
Then, intramolecular 1,8-addition gives intermediate
E and successive cleavage of the C O bond, and
proton transfer affords 2-functionalized aminotro-
pones 3.
À
1
1348C, Rf =0.5 (MeOH:CHCl3 =1:20), H NMR (400 MHz,
CDCl3): d=7.58 (d, J=11.8 Hz, 2H), 7.47–7.41 (m, 4H),
7.15 (d, J=8.6 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3):
Conclusions
d=171.0, 162.9 (d, JC,F =248.1 Hz), 141.5, 138.8 (d, JC,F
3.6 Hz), 137.7, 129.4 (d, JC,F =8.3 Hz), 124.2, 116.1 (d, JC,F
=
=
In conclusion, we have developed the Rh-catalyzed
reaction of tropolones with N-tosyl-1,2,3-triazoles for
the synthesis of the 2-functionalized aminotropones
via tandem Rh-catalyzed O H insertion, intramolecu-
lar 1,8-addition, and rearrangement in one pot. Se-
21.8 Hz); 19F NMR (376 MHz, CDCl3): d=À113.9; IR
(film): n=3202, 1564, 1506, 1459, 1424, 1274, 1213, 832; HR-
MS (FAB): m/z=217.0667, calcd. for C13H10O2F [M+H]+:
217.0665.
À
5-(4-Methoxyphenyl)tropolone (1e): Green solid; mp
158–1618C, Rf =0.5 (MeOH:CHCl3 =1:20), 1H NMR
(400 MHz, CDCl3): d=7.60 (d, J=11.8 Hz, 2H), 7.44–7.40
(m, 4H), 6.98 (d, J=8.8 Hz, 2H), 3.86 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): d=170.8, 160.0, 142.3, 137.4,
135.1, 128.9, 124.4, 114.6, 55.6; IR (film): n=3209, 1613,
1551, 1512, 1458, 1426, 1258, 1210, 1180, 1028, 829; HR-MS
(FAB): m/z=229.0863, calcd. for C14H13O3 [M+H]+:
229.0865.
The N-sulfonyl-1,2,3-triazole substrates 2 were prepared
according to a reported procedure.[15] The analytical data of
compounds 2a,[10b] 2b,[15] 2c,[16] 2d,[10b] 2e,[17] 2g,[15] 2h,[6e] 2i,[15]
2j,[6e] 2l,[8] 2m,[10a] 2n,[10a] 2o,[18] 2p,[6e] 2q,[15] 2r,[10a] 2s,[19] 2t,[10b]
and 2u[10b] have already been reported.
quential Cu-catalyzed [3+2] cycloaddition, Rh-cata-
À
lyzed O H insertion, intramolecular 1,8-addition, and
rearrangement starting from 1-alkynes, N-sulfonyl
azides, and tropolones is also demonstrated for the
synthesis of the 2-functionalized aminotropones in
one pot. These results suggest that sequential func-
tionalization of O H and C(sp ) O bonds smoothly
take place in C(sp ) O H bonds at the 2-position of
tropolone.
2
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À
2
À À
1-Tosyl-4-(m-tolyl)-1H-1,2,3-triazole (2f): Pale grey solid;
mp 102–1048C, Rf =0.5 (EtOAc:hexane=1:4); 1H NMR
(400 MHz, CDCl3): d=8.29 (s, 1H), 8.03 (d, J=2.8 Hz, 2H),
7.66 (s, 1H), 7.60 (d, J=7.7 Hz, 1H), 7.39 (d, J=8.0 Hz,
2H), 7.34 (t, J=7.7 Hz, 1H), 7.19 (d, J=7.6 Hz, 1H), 2.45
(s, 3H), 2.39 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=
147.5, 147.3, 138.8, 133.1 130.5, 129.9, 128.9, 128.7, 126.7,
123.2, 118.9, 21.9, 21.4; IR (film): n=3141, 1347, 1196, 1176,
960, 786, 671 cmÀ1; HR-MS (EI): m/z=313.0886, calcd. for
C16H15N3O2S: 313.0885.
1-Tosyl-4-(m-chlorophenyl)-1H-1,2,3-triazole (2k): White
solid; mp 100–1028C; Rf =0.5 (EtOAc:hexane=1:5);
1H NMR (400 MHz, CDCl3): d=8.33 (s, 1H), 8.03 (d, J=
8.1 Hz, 2H), 7.83 (s, 1H), 7.71 (d, J=6.6 Hz, 1H), 7.41–7.33
(m, 4H), 2.46 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=
147.6, 146.1, 135.0, 132.9, 130.6, 130.5, 130.3, 129.1, 128.8,
126.2, 124.2, 119.4, 21.9; IR (film): n=3143, 1393, 1347,
1196, 1177, 996, 768, 672 cmÀ1; HR-MS (EI): m/z=333.0336,
calcd. for C15H12ClN3O2S: 333.0339.
Experimental Section
General Information
Reactions were carried out in oven-dried glassware under
nitrogen atmosphere. Copper(I) thiophene-2-carboxylate
(CuTC), Rh2(OAc)4, Rh2(esp)2, and Rh2(OPiv)4 were pur-
chased and used as received. Commercially available re-
agents were used without purification. DCE, CHCl3,
EtOAc, 1,4-dioxane, cyclohexane, benzene, toluene, and
chlorobenzene were dried with CaH2. All reaction mixtures
were stirred magnetically and were monitored by thin-layer
chromatography using silica gel pre-coated glass plates,
which were visualized with UV light and then developed
using a solution of anisaldehyde. Flash column chromatogra-
phy was carried out using silica gel (230–400 mesh).
1H NMR (400 MHz) and 13C{1H} NMR (100 MHz), and
19F NMR (376 MHz) spectra were recorded on NMR spec-
trometers. Deuterated chloroform and DMSO were used as
the solvents, and chemical shift values (d) are reported in
parts per million relative to the residual signals of solvent
1
1
[d=7.26 for H (chloroform-d), d=2.50 for H (DMSO-d6),
d=77.16 for 13C{1H} (chloroform-d), and d=39.52 for
13C{1H} (DMSO-d6). Infrared spectra were recorded on an
FT-IR spectrometer as either a thin film pressed between
two sodium chloride plates or as a solid suspended in a po-
tassium bromide disk. High resolution mass spectra (HR-
MS) were obtained by fast atom bombardment (FAB) using
a double focusing magnetic sector mass spectrometer and
electron impact (EI) ionization technique (magnetic sector –
electric sector double focusing mass analyzer) from the
KBSI (Korea Basic Science Institute). Melting points were
determined in open capillary tube.
Synthesis of 2-Functionalized Aminotropones using
N-Sulfonyl-1,2,3-triazoles and Tropolones
DCE (1.0 mL) was added to a mixture of Rh2(OAc)4
(1.0 mol%), N-tosyl-1,2,3-triazole 2 (0.2 mmol) and tropo-
lone 1 (0.24 mmol) in an oven-dried test tube equipped with
a stir bar. The mixture was stirred for 1 h at 808C until 2
was completely consumed by TLC monitoring. Then, the re-
action mixture was washed with saturated Na2CO3 to
remove tropolone 1, and extracted with DCM (3”15 mL).
The combined organic phase was dried over MgSO4 and
concentrated under reduced pressure. The residue was puri-
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Sequential Functionalization of the O H and C(sp ) O Bonds
fied by silica gel flash column chromatography (EtOAc/
hexane) to give compound 3 as a solid; yield: 55–98%.
4-Methyl-N-(2-oxo-2-phenylethyl)-N-(7-oxocyclohepta-
1,3,5-trienyl)benzenesulfonamide (3aa): Reaction time: 1 h;
yield: 75 mg (95%); yellow solid; mp 146–1488C; Rf =0.2
(EtOAc:hexane=1:2); 1H NMR (400 MHz, CDCl3): d=
8.20–8.17 (m, 1H), 7.93–7.90 (m, 2H), 7.67 (d, J=8.3 Hz,
2H), 7.60–7.55 ( m, 1H), 7.45 (t, J=7.7 Hz, 2H), 7.26 (d, J=
8.0 Hz, 2H), 7.15–7.07 (m, 3H), 7.03–7.00 (m, 1H), 5.21 (s,
2H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=
194.3, 182.7, 146.9, 143.8, 143.0, 142.0, 137.0, 136.2, 135.6,
135.0, 133.8, 132.4, 129.6, 128.9, 128.1, 127.7, 53.7, 21.8; IR
(film): n=3063, 2925, 1699, 1631, 1594, 1519, 1495, 1465,
1223, 1159, 1093, 836, 814, 753 cmÀ1; HR-MS (FAB): m/z=
394,1115, calcd. for C22H20NO4S [M+H]+: 394.1113.
4-Methoxy-N-(2-oxo-2-phenylethyl)-N-(7-oxocyclohepta-
1,3,5-trienyl)benzenesulfonamide (3ab): Reaction time: 2 h;
yield: 69.2 mg (85%); yellow solid; mp 155–1578C; Rf =0.4
(EtOAc:hexane=1:1); 1H NMR (400 MHz, CDCl3): d=
8.19–8.17 (m, 1H), 7.93–7.90 (m, 2H), 7.73 (d, J=9.0 Hz,
2H), 7.58 (t, J=7.4 Hz, 1H), 7.45 (t, J=7.7 Hz, 2H), 7.16–
7.07 (m, 3H), 7.02 (d, J=11.8 Hz, 1H), 6.93 (d, J=9.0 Hz,
2H), 5.21 (s, 2H), 3.86 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): d=194.4, 182.7, 163.2, 147.0, 143.0, 142.0, 136.2,
135.6, 135.0, 133.8, 132.4, 131.6, 129.9, 128.9, 128.1, 114.1,
55.7, 53.7; IR (film): n=3062, 2934, 1690, 1600, 1465, 1421,
1346, 1263, 1234, 1161, 1094, 827, 811, 781, 734 cmÀ1; HR-
MS (FAB): m/z=410.1064, calcd. for C22H20NO5S [M+H]+:
410 1062.
2H), 3.23 (septet, J=6.7 Hz, 1H), 1.45 (d, J=6.8 Hz, 6H);
13C{1H} NMR (100 MHz, CDCl3): d=194.4, 183.4, 147.5,
143.6, 141.9, 136.6, 135.8, 134.9, 133.8, 132.8, 128.9, 128.0,
56.2, 54.7; IR (film): n=3063, 2935, 1700, 1630, 1583, 1467,
1449, 1335, 1223, 1180, 1142, 1096, 833, 781, 754 cmÀ1; HR-
MS (FAB): m/z=346.1112, calcd. for C18H20NO4S [M+H]+:
346.1113.
4-Methyl-N-(2-oxo-2m-tolylethyl)-N-(7-oxocyclohepta-
1,3,5-trienyl)benzenesulfonamide (3af): Reaction time: 2 h;
yield: 79.4 mg (97%); yellow solid; mp 95–978C; Rf =0.2
(EtOAc:hexane=1:2), 1H NMR (400 MHz, CDCl3): d=
8.21–8.15 (m, 1H), 7.71–7.66 (m, 4H), 7.39–7.31 (m, 2H),
7.26 (d, J=8.0 Hz, 2H), 7.17–7.07 (m, 3H), 7.01 (d, J=
11.7 Hz, 1H), 5.20 (s, 2H), 2.41 (s, 3H), 2.38 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): d=194.4, 182.6, 146.9,
143.8, 143.0, 142.0, 138.7, 137.0, 136.2, 135.6, 134.9, 134.5,
132.4, 129.5, 128.7, 128.6, 127.7, 125.2, 53.7, 21.7, 21.4; IR
(film): n=3063, 2924, 1697, 1631, 1589, 1465, 1347, 1254,
1161, 1094, 781, 731 cmÀ1; HR-MS (FAB): m/z=408.1266,
calcd. for C23H22NO4S [M+H]+: 408.1270.
4-Methyl-N-(2-oxo-2-p-tolylethyl)-N-(7-oxocyclohepta-
1,3,5-trienyl)benzenesulfonamide (3ag): Reaction time: 1 h;
yield: 78.2 mg (96%); light brown solid; mp 128–1308C;
1
Rf =0.1 (EtOAc:hexane=1:2); H NMR (400 MHz, CDCl3):
d=8.19–8.16 (m, 1H), 7.81 (d, J=8.2 Hz, 2H), 7.67 (d, J=
8.3 Hz, 2H), 7.27–7.23 (m, 4H), 7.15–7.07 (m, 3H), 7.03–
7.00 (m, 1H), 5.18 (s, 2H), 2.41(s, 3H), 2.40 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): d=193.9, 182.7, 147.0, 144.7,
143.8, 143.0, 142.0, 137.1, 136.1, 135.6, 132.5, 132.4, 129.5,
128.2, 127.7, 53.5, 21.84, 21.75; IR (film): n=3033, 2924,
1696, 1631, 1593, 1465, 1410, 1327, 1179, 1160, 1094, 807,
779, 730 cmÀ1; HR-MS (FAB): m/z=408.1273, calcd. for
C23H22NO4S [M+H]+: 408.1270.
N-(2-Oxo-2-phenylethyl)-N-(7-oxocyclohepta-1,3,5-trien-
yl)-4-(trifluoromethyl)benzenesulfonamide (3ac): Reaction
time: 1 h; yield: 63.6 mg (71%); yellow solid; mp 147–
1
1498C; Rf =0.7 (EtOAc:hexane=1:1); H NMR (400 MHz,
CDCl3): d=8.21–8.18 (m, 1H), 7.94–7.90 (m, 4H), 7.74 (d,
J=8.3 Hz, 2H), 7.61–7.57 (m, 1H), 7.47 (t, J=7.7 Hz, 2H),
7.21–7.11 (m, 3H), 7.05–7.02 (m, 1H), 5.20 (s, 2H); 13C{1H}
NMR (100 MHz, CDCl3): d=193.7, 182.5, 146.4, 143.5,
142.1, 136.5, 136.2, 134.8, 134.6 (q, JC,F =33.0 Hz), 134.4,
134.0, 132.4, 129.0, 128.3, 128.1, 126.1 (q, JC,F =3.6 Hz), 123.4
(q, JC,F =273.0 Hz), 54.0; 19F NMR (376 MHz, CDCl3): d=
À63.0; IR (film): n=3064, 2931, 1701, 1632, 1594, 1466,
N-[2-(2-Methoxyphenyl)-2-oxoethyl]-4-methyl-N-(7-oxo-
cyclohepta-1,3,5-trienyl)benzenesulfonamide (3ah): Reac-
tion time: 1 h; yield: 74.8 mg (88%); light brown solid; mp
129–1318C;
Rf =0.1
(EtOAc:hexane=1:2),
1H NMR
(400 MHz, CDCl3): d=8.10–8.07 (m, 1H), 7.77 (dd, J=7.8,
1.8 Hz, 1H), 7.66 (d, J=8.3 Hz, 2H), 7.47 (ddd, J=8.4, 7.3,
1.8 Hz, 1H), 7.24 (d, J=8.0 Hz, 2H), 7.15- 7.09 (m, 1H),
7.06–6.97 (m, 4H), 6.93 (d, J=8.3 Hz, 1H), 5.08 (s, 2H),
3.86 (s, 3H), 2.40 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
d=196.2, 182.7, 159.1, 147.5, 143.5, 142.4, 141.9, 137.3, 135.9,
135.2, 134.4, 132.4, 131.0, 129.4, 127.8, 125.7, 120.9, 111.5,
58.0, 55.6, 21.7; IR (film): n=3065, 2945, 1684, 1631, 1596,
1485, 1465, 1346, 1285, 1245, 1160, 1093, 1020, 991, 835, 815,
761, 733 cmÀ1; HR-MS (FAB): m/z=424.1217, calcd. for
C23H22NO5S [M+H]+: 424.1219.
1449, 1405, 1355, 1323, 1166, 1132, 1107, 1063, 837, 753 cmÀ1
;
HR-MS (FAB): m/z=448.0831, calcd. for C22H17F3NO4S
[M+H]+: 448.0830.
N-(2-Oxo-2-phenylethyl)-N-(7-oxocyclohepta-1,3,5-trien-
yl)methanesulfonamide (3ad): Reaction time: 1 h; yield:
56 mg (88%); yellow solid; mp 98–1008C; Rf =0.4 (EtOA-
c:hexane=1:1); 1H NMR (400 MHz, CDCl3): d=8.15–8.12
(m, 1H), 7.93(d, J=7.3 Hz, 2H), 7.59 (t, J=7.4 Hz, 1H),
7.46 (t, J=7.7 Hz, 2H), 7.27–7.10 (m, 4H), 5.14 (s, 2H), 3.08
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=193.9, 183.3,
147.2, 143.8, 142.1, 136.8, 136.2, 134.7, 133.9, 132.7, 128.9,
128.1, 53.6, 41.0; IR (film): n=3041, 2959, 1699, 1578, 1463,
1422, 1335, 1252, 1221, 1180, 1150, 750, 736, 687 cmÀ1; HR-
MS (FAB): m/z=318.0798, calcd. for C16H15NO4S [M+H]+:
318.0800.
N-(2-Oxo-2-phenylethyl)-N-(7-oxocyclohepta-1,3,5-trien-
yl)propane-2-sulfonamide (3ae): Reaction time: 2 h; yield:
51.5 mg (75%); yellow solid; mp 121–1238C; Rf =0.5
(EtOAc:hexane=1:1); 1H NMR (400 MHz, CDCl3): d=
8.35–8.32 (m, 1H), 7.91 (d, J=8.2 Hz, 2H), 7.59–7.55 (m,
1H), 7.45 (t, J=7.6 Hz, 2H), 7.27–7.13 (m, 4H), 5.23 (s,
N-[2-(4-Methoxyphenyl)-2-oxoethyl]-4-methyl-N-(7-oxo-
cyclohepta-1,3,5-trienyl)benzenesulfonamide (3ai): Reaction
time: 3 h; yield: 83.1 mg (98%); yellow solid; mp 68–708C;
1
Rf =0.4 (EtOAc:hexane=1:1); H NMR (400 MHz, CDCl3):
d=8.18–8.15 (m, 1H), 7.90 (d, J=9.0 Hz, 2H), 7.67 (d, J=
8.3 Hz, 2H), 7.26 (d, J=7.7 Hz, 2H), 7.16–7.06 (m, 3H),
7.01 (d, J=11.8 Hz, 1H), 6.91 (d, J=9.0 Hz, 2H), 5.15 (s,
2H), 3.86 (s, 3H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): d=192.7, 182.7, 164.0, 147.0, 143.8, 143.0, 142.0,
137.1, 136.1, 135.6, 132.4, 130.4, 129.5, 128.0, 127.7, 114.0,
55.6, 53.2, 21.8; IR (film): n=3067, 2928, 1693, 1629, 1586,
1499, 1464, 1447, 1340, 1256, 1157, 1092, 826, 747 cmÀ1; HR-
MS (FAB): m/z=424.1216, calcd. for C23H22NO5S [M+H]+:
424.1219.
Adv. Synth. Catal. 2016, 358, 1078 – 1087
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1083

FULL PAPERS
Boram Seo et al.
N-[2-(4-Fluorophenyl)-2-oxoethyl]-4-methyl-N-(7-oxocy-
clohepta-1,3,5-trienyl)benzenesulfonamide (3aj): Reaction
time: 1 h; yield: 59.8 mg (68%); light brown solid; mp 140–
8.1 Hz, 2H), 7.73 (d, J=8.2 Hz, 2H), 7.65 (d, J=8.3 Hz,
2H), 7.26 (d, J=8.0 Hz, 2H), 7.19–7.10 (m, 3H), 7.03–6.99
(m, 1H), 5.21 (s, 2H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): d=193.6, 182.6, 146.7, 144.0, 143.0, 142.0, 137.7,
136.7, 136.3, 135.8, 135.5, 135.0 (q, JC,F =32.8 Hz), 132.4,
1
1428C; Rf =0.1 (EtOAc:hexane=1:2); H NMR (400 MHz,
CDCl3): d=8.18–8.16 (m, 1H), 7.97–7.94 (m, 2H), 7.66 (d,
J=8.3 Hz, 2H), 7.26 (d, J=7.2 Hz, 2H), 7.15–7.08 (m, 5H),
7.03–7.00 (m, 1H) 5.17 (s, 2H), 2.41 (s, 3H); 13C{1H} NMR
129.6, 128.5, 127.7, 125.9 (q, JC,F =3.7 Hz), 123.6 (q, JC,F
=
272.9 Hz), 53.9, 21.7; 19F NMR (376 MHz, CDCl3): d=
À63.3; IR (film): n=3066, 2925, 1707, 1631, 1592, 1513,
1466, 1346, 1326, 1161, 1130, 1094, 1066, 825, 813 cmÀ1; HR-
MS (FAB): m/z=462.0985, calcd. for C23H19F3NO4S [M+
H]+: 462.0987.
(100 MHz, CDCl3): d=192.8, 182.6, 166.1 (d, JC,F
=
255.7 Hz), 146.8, 143.9, 143.6, 142.0, 136.9, 136.2, 135.7,
132.4, 131.4 (d, JC,F =2.9 Hz), 130.8 (d, JC,F =9.4 Hz), 129.6,
127.7, 116.1 (d,
J
C,F =22.0 Hz), 53.5, 21.8; 19F NMR
(376 MHz, CDCl3): d=À103.8; IR (film): n=3063, 2952,
1724, 1704, 1631, 1692, 1436, 1407, 1348, 1281, 1160, 1108,
829, 780, 762, 730 cmÀ1; HR-MS (FAB): m/z=412.1022,
calcd. for C22H19FNO4S [M+H]+: 412.1019.
N-[2-(4-Acetylphenyl)-2-oxoethyl]-4-methyl-N-(7-oxocy-
clohepta-1,3,5-trienyl)benzenesulfonamide (3ao): Reaction
time: 3 h; yield: 78.4 mg (90%); brown solid; mp 150–
1
1528C; Rf =0.3 (EtOAc:hexane=1:1); H NMR (400 MHz,
N-[2-(3-Chlorophenyl)-2-oxoethyl]-4-methyl-N-(7-oxocy-
clohepta-1,3,5-trienyl)benzenesulfonamide (3ak): Reaction
time: 3 h; yield: 77.5 mg (91%); yellow solid; mp 142–
CDCl3): d=8.18–8.15 (m, 1H), 8.03–7.98 (m, 4H), 7.65 (d,
J=8.3 Hz, 2H), 7.26 (d, J=8.5 Hz, 2H), 7.19–7.09 (m, 3H),
7.01 (d, J=11.5 Hz, 1H), 5.22 (s, 2H), 2.64 (s, 3H), 2.42 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): d=197.4, 194.0,
182.6, 146.7, 144.0, 143.0, 141.0, 140.6, 138.1, 136.7, 136.3,
135.8, 132.4, 129.6, 128.7, 128.3, 127.7, 54.0, 27.0, 21.7; IR
(film): n=3064, 2925, 1687, 1592, 1501, 1465, 1348, 1263,
1221, 1160, 1094, 813, 728 cmÀ1; HR-MS (FAB): m/z=
436.1216, calcd. for C24H22NO5S [M+H]+: 436.1219.
1
1448C; Rf =0.2 (EtOAc:hexane=1:2); H NMR (400 MHz,
CDCl3): d=8.18–8.16 (m, 1H), 7.87 (t, J=1.8 Hz, 1H), 7.80
(dt, J=7.8, 1.3 Hz, 1H), 7.65 (d, J=8.3 Hz, 2H), 7.56–7.53
(m, 1H), 7.40 (t, J=7.9 Hz, 1H), 7.26 (d, J=8.0 Hz, 2H),
7.18–7.10 (m, 3H), 7.03–7.00 (m, 1H), 5.17 (s, 2H), 2.41 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): d=193.2, 182.6,
146.7, 144.0, 143.1, 142.0, 136.8, 136.4, 136.3, 135.8, 135.2,
133.7, 132.4, 130.2, 129.6, 128.2, 127.7, 126.2, 53.7, 21.8; IR
(film): n=3065, 2925, 1704, 1631, 1593, 1519, 1495, 1417,
1348, 1219, 1189, 1160, 1093, 782, 737 cmÀ1; HR-MS (FAB):
m/z=428.0720, calcd. for C22H19ClNO4S [M+H]+: 428.0723.
N-[2-(2-Bromophenyl)-2-oxoethyl]-4-methyl-N-(7-oxocy-
clohepta-1,3,5-trienyl)benzenesulfonamide (3al): Reaction
time: 10 h; yield: 45.3 mg (48%); brown solid; mp 106–
Methyl 4-{2-[4-methyl-N-(7-oxocyclohepta-1,3,5-trienyl)-
phenylsulfonamido]acetyl}benzoate (3ap): Reaction time:
3 h; yield: 69.1 mg (77%); light brown solid; mp 72–758C;
1
Rf =0.1 (EtOAc:hexane=1:2); H NMR (400 MHz, CDCl3):
d=8.19–8.16 (m, 1H), 8.11 (d, J=8.3 Hz, 2H), 7.97 (d, J=
8.5 Hz, 2H), 7.67 (d, J=8.3 Hz, 2H), 7.26 (d, J=8.0 Hz,
2H), 7.18–7.09 (m, 3H), 7.01 (d, J=11.5 Hz, 1H), 5.21 (s,
2H), 3.95 (s, 3H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): d=194.0, 182.6, 166.1, 146.7, 144.0, 143.0, 142.0,
138.2, 136.8, 136.2, 135.8, 134.5, 132.4, 130.0, 129.6, 128.0,
127.7, 54.0, 52.6, 21.8; IR (film): n=3067, 2925, 1699, 1631,
1596, 1507, 1465, 1346, 1226, 1159, 1093, 827, 672 cmÀ1; HR-
MS (FAB): m/z=452.1166, calcd. for C24H22NO6S [M+H]+:
452.1168.
1
1088C; Rf =0.1 (EtOAc:hexane=1:2); H NMR (400 MHz,
CDCl3): d=7.87 (dd, J=8.9, 1.2 Hz, 1H), 7.62 (d, J=8.3 Hz,
2H), 7.56 (dd, J=7.9, 0.8 Hz, 1H), 7.50 (dd, J=7.6, 1.7 Hz,
1H), 7.40 (td, J=7.5, 1.0 Hz, 1H), 7.30 (td, J=11.5, 1.7 Hz,
1H), 7.24 (d, J=8.4 Hz, 2H), 7.19–7.00 (m, 4H), 4.98 (s,
2H), 2.40 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=
198.8, 182.6, 146.7, 144.0, 142.5, 141.9, 139.4, 136.6, 136.2,
135.6, 133.6, 132.3, 132.2, 129.6, 129.4, 127.7, 127.6, 119.0,
56.2, 21.8; IR (film): n=3063, 2923, 1713, 1631, 1588, 1466,
1428, 1348, 1160, 1092, 1053, 813, 758, 733, 671 cmÀ1; HR-
MS (FAB): m/z=472.0220, calcd. for C22H19BrNO4S [M+
H]+: 472.0218.
4-Methyl-N-[2-(naphthalen-2-yl)-2-oxoethyl]-N-(7-oxocy-
clohepta-1,3,5-trienyl)benzenesulfonamide (3aq): Reaction
time: 2 h; yield: 78.7 mg (89%); light brown solid; mp 72–
758C; Rf =0.2 (EtOAc:hexane=1:2); 1H NMR (400 MHz,
CDCl3): d=8.45 (s, 1H), 8.23–8.21 (m, 1H), 7.98–7.93 (m,
2H), 7.89–7.85 (m, 2H), 7.70 (d, J=8.3 Hz, 2H), 8.63–7.54
(m, 2H), 7.28 (d, J=8.0 Hz, 2H), 7.18–7.08 (m, 3H), 7.05–
7.02 (m, 1H), 5.35 (s, 2H), 2.42 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): d=194.2, 182.7, 147.0, 143.9, 143.1,
142.0, 137.1, 136.2, 135.9, 135.7, 132.5, 132.2, 129.9, 129.7,
129.6, 128.9, 128.8, 127.9, 127.8, 127.1, 123.6, 53.7, 21.8; IR
(film): n=3060, 2925, 1693, 1629, 1593, 1518, 1494, 1467,
1347, 1160, 1093, 813, 780, 734, 672 cmÀ1; HR-MS (FAB): m/
z=444.1271, calcd. for C26H22NO4S [M+H]+: 444.1270.
4-Methyl-N-[2-oxo-2-(thiophen-3-yl)ethyl]-N-(7-oxocyclo-
hepta-1,3,5-trienyl)benzenesulfonamide (3ar): Reaction
time: 1 h; yield: 44.1 mg (55%); light brown solid; mp 185–
N-[2-(4-Bromophenyl)-2-oxoethyl]-4-methyl-N-(7-oxocy-
clohepta-1,3,5-trienyl)benzenesulfonamide (3am): Reaction
time: 8 h; yield: 81.6 mg (86%); light brown solid; mp 146–
1
1488C; Rf =0.2 (EtOAc:hexane=1:2); H NMR (400 MHz,
CDCl3): d=8.17–8.15 (m, 1H), 7.78 (d, J=8.6 Hz, 2H), 7.65
(d, J=8.3 Hz, 2H), 7.60 (d, J=8.7 Hz, 2H), 7.26 (d, J=
7.9 Hz, 2H), 7.17–7.08 (m, 3H), 7.01 (d, J=11.6 Hz, 1H),
5.15 (s, 2H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
d=193.4, 182.6, 146.8, 144.0, 143.0, 142.0, 136.8, 136.2, 135.7,
133.7, 132.4, 132.3, 129.6, 129.1, 127.7, 53.6, 21.8; IR (film):
n=3063, 2925, 1700, 1631, 1585, 1496, 1467, 1347, 1160,
1093, 1071, 812, 733, 672 cmÀ1; HR-MS (FAB): m/z=
472.0217, calcd. for C22H19BrNO4S [M+H]+: 472.0218.
4-Methyl-N-{2-oxo-2-[4-(trifluoromethyl)phenyl]ethyl}-N-
1
1888C; Rf =0.1 (EtOAc:hexane=1:2); H NMR (400 MHz,
CDCl3): d=8.15–8.11 (m, 2H), 7.66 (d, J=8.3 Hz, 2H), 7.52
(dd, J=5.1, 1.2 Hz, 1H), 7.32 (dd, J=5.1, 2.8 Hz, 1H), 7.26
(d, J=7.8 Hz, 2H), 7.17–7.07 (m, 3H), 7.02 (d, J=11.8 Hz,
1H), 5.07 (s, 2H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): d=188.7, 182.9, 146.9, 143.9, 143.0, 142.0, 139.5,
137.0, 136.2, 135.7, 132.5, 132.4, 129.6, 127.7, 126.8, 54.0,
(7-oxocyclohepta-1,3,5-trienyl)benzenesulfonamide
Reaction time: 2 h; yield: 66.7 mg (72%); yellow solid; mp
167–1698C, Rf =0.3 (EtOAc:hexane=1:2),
1H NMR
(400 MHz, CDCl3): d=8.18–8.16 (m, 1H), 8.03 (d, J=
(3an):
1084
asc.wiley-vch.de
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2016, 358, 1078 – 1087

2
À
À
FULL PAPERS
Sequential Functionalization of the O H and C(sp ) O Bonds
21.8; IR (film): n=3105, 2924, 1690, 1630, 1591, 1510, 1465,
1347, 1160, 1093, 783, 672 cmÀ1; HR-MS (FAB): m/z=
400.0675, calcd. for C20H18NO4S2 [M+H]+: 400.0677.
(400 MHz, CDCl3): d=8.25 (d, J=10.0 Hz, 1H), 7.91 (d, J=
9.0 Hz, 2H), 7.71 (d, J=8.3 Hz, 2H), 7.51–7.41 (m, 6H),
7.28–7.23 (m, 3H), 7.10 (d, J=12.7 Hz, 1H), 6.92 (d, J=
8.9 Hz, 2H), 5.20 (s, 2H), 3.86 (s, 3H), 2.42 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): d=192.8, 182.0, 164.0, 149.1,
145.3, 143.8, 143.1, 141.8, 141.4, 137.8, 137.2, 130.4, 129.6,
129.23, 129.21, 128.0, 127.8, 127.5, 114.0, 55.6, 53.3, 21.8; IR
(film): n=3060, 2933, 1689, 1627, 1599, 1512, 1346, 1263,
1233, 1160, 1091, 827, 768, 698 cmÀ1; HR-MS (FAB): m/z=
500.1534, calcd. for C29H26NO5S [M+H]+: 500.1532.
4-Methyl-N-(7-oxocyclohepta-1,3,5-trienyl)-N-(2-oxohex-
yl)benzenesulfonamide (3as): Reaction time: 1 h; yield:
54 mg (72%); brown solid; mp 60–638C; Rf =0.4
1
(EtOAc:DCM:hexane=1:1:2); H NMR (400 MHz, CDCl3):
d=8.07–8.04 (m, 1H), 7.60 (d, J=8.3 Hz, 2H), 7.24 (d, J=
8.0 Hz, 2H), 7.18–7.07 (m, 3H), 6.98 (d, J=11.6 Hz, 1H),
4.48 (s, 2H), 2.39 (s, 3H), 1.53 (quintet, J=7.5 Hz, 2H), 1.28
(sextet, J=7.4 Hz, 2H), 0.87 (t, J=7.3 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3): d=205.7, 182.5, 146.8, 143.8,
142.3, 141.8, 136.5, 136.1, 135.5, 132.3, 129.4, 127.6, 56.2,
39.4, 25.5, 22.2, 21.6, 13.8; IR (film): n=3031, 2957, 2931,
N-(4-Bromo-7-oxocyclohepta-1,3,5-trienyl)-4-methyl-N-(2-
oxo-2-phenylethyl)benzenesulfonamide (3ca): Reaction
time: 4 h; yield: 67.1 mg (71%); yellow solid; mp 157–
1
1598C; Rf =0.3 (EtOAc:hexane=1:2); H NMR (400 MHz,
2871, 1729, 1593, 1465, 1347, 1161, 1090, 813, 781, 664 cmÀ1
;
CDCl3): d=7.92–7.89 (m, 3H), 7.66 (d, J=8.3 Hz, 2H), 7.58
(t, J=7.4 Hz, 1H), 7.47–7.43 (m, 3H), 7.33 (dd, J=12.9,
2.1 Hz, 1H), 7.27 (d, J=8.1 Hz, 2H), 6.78 (d, J=12.9 Hz,
1H), 5.81 (s, 2H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): d=194.1, 181.7, 146.1, 144.1, 141.5, 140.6, 140.2,
136.8, 134.8, 134.3, 133.9, 132.4, 129.7, 128.9, 128.1, 127.7,
53.5, 21.8; IR (film): n=3061, 2927, 1699, 1620, 1582, 1507,
1448, 1349, 1161, 849, 813 cmÀ1; HR-MS (FAB): m/z=
472.0216, calcd. for C22H19BrNO4S [M+H]+: 472.0218.
N-(4-Bromo-7-oxocyclohepta-1,3,5-trienyl)-N-[2-(4-me-
thoxyphenyl)-2-oxoethyl]-4-methylbenzenesulfonamide
(3ci): Reaction time: 3 h; yield: 95.6 mg (95%); yellow solid;
mp 132–1348C; Rf =0.6 (EtOAc:DCM:hexane=1:1:2);
1H NMR (400 MHz, CDCl3): d=7.89–7.87 (m, 3H), 7.66 (d,
J=8.3 Hz, 2H), 7.44 (dd, J=10.3, 1.9 Hz, 1H), 7.32 (dd, J=
12.9, 2.1 Hz, 1H), 7.26 (d, J=8.0 Hz, 2H), 6.91 (d, J=
8.9 Hz, 2H), 6.77 (d, J=12.9 Hz, 1H), 5.13 (s, 2H), 3.85 (s,
3H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=
192.5, 181.7, 164.1, 146.2, 144.0, 141.4, 140.6, 140.1, 136.9,
134.3, 132.3, 130.4, 129.6, 127.8, 127.7, 114.1, 55.6, 53.1, 21.7;
IR (film): n=3062, 2934, 2841, 1689, 1620, 1600, 1422, 1348,
1263, 1233, 1161, 1091, 812, 732 cmÀ1; HR-MS (FAB): m/z=
502.0322, calcd. for C23H21BrNO5S [M+H]+: 502.0324.
N-(4-Bromo-7-oxocyclohepta-1,3,5-trienyl)-N-[2-(3-chlor-
HR-MS (FAB): m/z=374.1424, calcd. for C20H24NO4S [M+
H]+: 374.1426.
4-Methyl-N-(2-oxo-3-phenylpropyl)-N-(7-oxocyclohepta-
1,3,5-trienyl)benzenesulfonamide (3at): Reaction time: 1 h;
yield: 52.4 mg (65%); light brown solid; mp 65–688C; Rf =
1
0.1 (EtOAc:hexane=1:2); H NMR (400 MHz, CDCl3): d=
8.01–7.98 (m, 1H), 7.55 (d, J=8.3 Hz, 2H), 7.32–7.23 (m,
3H), 7.21 (d, J=8.3 Hz, 2H), 7.15 (d, J=7.0 Hz, 2H), 7.13–
7.08 (m, 1H), 7.06–7.00 (m, 2H), 6.95 (d, J=11.7 Hz, 1H),
4.54 (s, 2H), 3.74 (s, 2H), 2.38 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): d=202.9, 182.5, 146.8, 143.9, 142.3,
141.8, 136.4, 136.1, 135.6, 133.1, 132.3, 129.58, 129.50, 128.8,
127.7, 127.3, 55.9, 46.9, 21.7; IR (film): n=3030, 2923, 1732,
1631, 1592, 1496, 1465, 1455, 1347, 1160, 1091, 1050, 781,
729, 701 cmÀ1; HR-MS (FAB): m/z=408.1271, calcd. for
C23H22NO4S [M+H]+: 408.1270.
N-(2-Cyclohexenyl-2-oxoethyl)-4-methyl-N-(7-oxocyclo-
hepta-1,3,5-trienyl)benzenesulfonamide (3au): Reaction
time: 2 h; yield: 64.9 mg (82%); light brown solid; mp 142–
1
1458C; Rf =0.2 (EtOAc:hexane=1:2); H NMR (400 MHz,
CDCl3): d=8.15–8.12 (m, 1H), 7.63 (d, J=8.2 Hz, 2H), 7.23
(d, J=8.3 Hz, 2H), 7.15–7.05 (m, 3H), 7.00 (d, J=11.8 Hz,
1H), 6.89 (s, 1H), 4.88 (s, 2H), 2.39 (s, 3H), 2.20 (d, J=
14.3 Hz, 4H), 1.60–1.58 (m, 4H); 13C{1H} NMR (100 MHz,
CDCl3): d=194.8, 182.7, 147.1, 143.7, 143.1, 142.0, 141.0,
137.7, 137.2, 136.1, 135.4, 132.5, 129.5, 127.7, 52.4, 26.1, 23.0,
21.8, 21.7, 21.5; IR (film): n=3060, 2933, 1681, 1631, 1591,
ophenyl)-2-oxoethyl]-4-methylbenzenesulfonamide
(3ck):
Reaction time: 5 h; yield: 66.7 mg (66%); yellow solid; mp
1
145–1478C; Rf =0.7 (EtOAc:DCM:hexane=1:1:2), H NMR
(400 MHz, CDCl3): d=7.89 (d, J=10.3 Hz, 1H), 7.86 (t, J=
1.8 Hz, 1H), 7.78 (dt, J=7.8, 1.3 Hz, 1H), 7.64 (d, J=
8.3 Hz, 2H), 7.56–7.53 (m, 1H), 7.47 (dd, J=10.3, 2.0 Hz,
1H), 7.40 (t, J=7.9 Hz, 1H), 7.34 (dd, J=12.9, 2.1 Hz, 1H),
7.27 (d, J=8.0 Hz, 2H), 6.78 (d, J=12.8 Hz, 1H), 5.14 (s,
2H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=
193.0, 181.7, 145.9, 144.2, 141.5, 140.6, 140.3, 136.6, 136.3,
135.3, 134.3, 133.8, 132.6, 130.3, 129.7, 128.2, 127.7, 126.2,
53.6, 21.8; IR (film): n=3065, 2925, 1704, 1260, 1582, 1506,
1422, 1349, 1203, 1161, 1091, 848, 813, 730, 677 cmÀ1; HR-
MS (FAB): m/z=505.9830, calcd. for C22H18BrClNO4S [M+
H]+: 505.9828.
N-[4-(4-Fluorophenyl)-7-oxocyclohepta-1,3,5-trienyl)-N-
[2-(4-methoxyphenyl)-2-oxoethyl]-4-methylbenzenesulfon-
amide (3di): Reaction time: 2 h; yield: 86.5 mg (83%);
yellow solid; mp 198–2008C; Rf =0.5 (EtOAc:hexane=1:1);
1H NMR (400 MHz, CDCl3): d=8.24 (d, J=10.0 Hz, 1H),
7.91 (d, J=8.9 Hz, 2H), 7.70 (d, J=8.3 Hz, 2H), 7.49–7.46
(m, 2H), 7.38 (dd, J=12.7, 1.9 Hz, 1H), 7.27 (d, J=8.5 Hz,
2H), 7.20 (dd, J=10.1, 1.7 Hz, 1H), 7.16 (t, J=8.6 Hz, 2H),
7.09 (d, J=12.7 Hz, 1H), 6.92 (d, J=8.9 Hz, 2H), 5.19 (s,
1422, 1388, 1345, 1185, 1160, 1094, 814, 782, 722, 672 cmÀ1
;
HR-MS (FAB): m/z=398.1429, calcd. for C22H24NO4S [M+
H]+: 398.1426.
4-Methyl-N-(2-oxo-2-phenylethyl)-N-(7-oxo-4-phenylcy-
clohepta-1,3,5-trienyl)benzenesulfonamide (3ba): Reaction
time: 3 h; yield: 73.8 mg (79%); yellow solid; mp 91–938C;
1
Rf =0.6 (EtOAc:DCM:hexane=1:1:2); H NMR (400 MHz,
CDCl3): d=8.26 (d, J=10.0 Hz, 1H), 7.93 (d, J=7.3 Hz,
2H), 7.71 (d, J=8.3 Hz, 2H), 7.57 (t, J=7.4 Hz, 1H), 7.51–
7.42 (m, 8H), 7.29–7.24 (m, 3H), 7.10 (d, J=12.7 Hz, 1H),
5.25 (s, 2H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
d=194.3, 181.9, 149.2, 145.2, 143.8, 143.2, 141.8, 141.4, 137.9,
137.1, 135.0, 133.8, 130.4, 129.6, 129.3, 129.2, 128.9, 128.1,
127.7, 127.5, 53.7, 21.8; IR (film): n=3061, 2925, 1699, 1585,
1347, 1209, 1160, 1091 cmÀ1; HR-MS (FAB): m/z=470.1424,
calcd. for C28H24NO4S [M+H]+: 470.1426, found : .
N-[2-(4-Methoxyphenyl)-2-oxoethyl]-4-methyl-N-(7-oxo-
4-phenylcyclohepta-1,3,5-trienyl)benzenesulfonamide (3bi):
Reaction time: 2 h; yield: 82.2 mg, (82%); orange solid; mp
97–998C;
Rf =0.7
(EtOAc:hexane=1:1);
1H NMR
Adv. Synth. Catal. 2016, 358, 1078 – 1087
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1085

FULL PAPERS
Boram Seo et al.
2H), 3.86 (s, 3H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): d=192.7, 181.9, 164.1, 163.5 (d, JC,F =250 Hz),
148.0, 145.5, 143.8, 143.0, 141.9, 137.60, 137.57, 137.2, 130.4,
130.3, 129.6, 129.4 (d, JC,F =8.3 Hz), 128.0, 127.8, 116.3 (d,
137.5, 136.7, 132.8, 132.5, 132.1, 129.8, 129.3, 128.8, 127.7,
126.4, 123.2, 114.9, 114.6, 21.0; IR (film): n=3262, 1665,
1618, 1546, 1491, 1472, 1330, 1256, 1150, 917, 859 cmÀ1; HR-
MS (FAB): m/z=394.1109, calcd. for C22H20NO4S [M+H]+:
394.1113.
J
C,F =21.9 Hz),114.1, 55.6, 53.3, 21.8; 19F NMR (376 MHz,
CDCl3): d=À112.0; IR (film): n=3065, 2934, 1689, 1599,
1507, 1346, 1234, 1161, 833, 732 cmÀ1; HR-MS (FAB): m/z=
518.1439, calcd. for C29H25FNO5S [M+H]+: 518.1437.
Synthesis of 2-Aminotropone 3aa from Reaction
Intermediate 3aa’
N-[2-(4-Methoxyphenyl)-2-oxoethyl]-N-[4-(4-methoxy-
phenyl)-7-oxocyclohepta-1,3,5-tri-enyl]-4-methylbenzenesul-
fonamide (3ei): Reaction time: 2 h; yield: 72.6 mg (68%);
orange solid; mp 93–958C; Rf =0.5 (EtOAc:hexane=1:1);
1H NMR (400 MHz, CDCl3): d=8.22 (d, J=10.1 Hz, 1H),
7.91 (d, J=9.0 Hz, 2H), 7.71 (d, J=8.3 Hz, 2H), 7.46–7.41
(m, 3H), 7.27 (d, J=8.0 Hz, 2H), 7.20 (dd, J=10.1, 1.6 Hz,
1H), 7.08 (d, J=12.7 Hz, 1H), 6.98 (d, J=8.8 Hz, 2H), 6.91
(d, J=9.0 Hz, 2H), 5.19 (s, 2H), 3.866 (s, 3H), 3.853 (s, 3H),
2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): d=192.8,
181.9, 164.0, 160.7, 148.8, 144.6, 143.7, 143.4, 141.8, 137.7,
137.2, 133.7, 130.4, 129.5, 129.2, 128.9, 128.1, 127.7, 114.7,
114.0, 55.6, 55.5, 53.3, 21.7; IR (film): n=2934, 1689, 1626,
1600, 1509, 1256, 1172, 1160, 830, 813 cmÀ1; HR-MS (FAB):
m/z=530.1641, calcd. for C30H28NO6S [M+H]+: 530.1637.
DCE (1.0 mL) was added to 4-methyl-N-[2-(7-oxocyclohep-
ta-1,3,5-trienyloxy)-2-phenylvinyl]benzenesulfonamide 3aa’
(0.2 mmol) in an oven-dried test tube equipped with a stir
bar. The mixture was stirred for 1 h at 808C under N2 until
3aa’ was completely consumed by TLC monitoring. The re-
sulting mixture was concentrated under reduced pressure
and purified by silica gel flash column chromatography
(EtOAc/hexane) to give compound of 3aa as a yellow solid;
yield: 72.6 mg (92%).
Acknowledgements
This work was supported by the National Research Founda-
tion of Korea (NRF) grant funded by the Korea government
(MSIP) (2011-0018355 and 2015H1CA1035955).
Synthesis of 2-Functionalized Aminotropones from
N-Tosyl Azide, 1-Alkynes, and Tropolone in One Pot
N-Tosyl azide 4 (0.2 mmol) was added to a mixture of
Rh2(OAc)4 (1.0 mol%), CuTC (10.0 mol%), 1-alkyne
5
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508C until 4 was completely consumed by TLC monitoring.
Then, tropolone 1a (0.24 mmol) in DCE (0.5 mL) was
added to the reaction mixture, which was further stirred for
3–7 h at 808C until 2 was completely consumed by TLC
monitoring. The resulting mixture was washed with saturat-
ed NH4Cl to remove CuTC and with saturated Na2CO3 to
remove tropolone 1a and extracted with DCM (3”15 mL).
The conbined organic phase was dried over MgSO4 and con-
centrated under reduced pressure. The residue was purified
by silica gel flash column chromatography (EtOAc/hexane)
to give compound 3 as a solid; yield: 51–70%.
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Toluene (1.0 mL) was added to a mixture of Rh2(OPiv)4
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4-Methyl-N-[2-(7-oxocyclohepta-1,3,5-trienyloxy)-2-phe-
nylvinyl]benzenesulfonamide (3aa’): Pale green solid; mp
180–1828C; Rf =0.1 (EtOAc:hexane=1:2); 1H NMR
(400 MHz, DMSO): d=10.40 (d, J=10.5 Hz, 1H), 7.78 (d,
J=8.3 Hz, 2H), 7.40 (d, J=8.1 Hz, 2H), 7.35–7.26 (m, 5H),
7.23–7.19 (m, 1H), 7.12 (d, J=12.2 Hz, 1H), 7.01 (d, J=
10.6 Hz, 1H), 6.90 (dd, J=10.6, 8.3 Hz, 1H), 6.81 (t, J=
10.1 Hz, 2H), 6.50 (d, J=9.5 Hz, 1H), 2.38 (s, 3H); 13C{1H}
NMR (100 MHz, DMSO): d=178.8, 161.9, 143.4, 137.7,
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