Gold catalysis: Anellated heterocycles and dependency of the reaction pathway on the tether length

Article abstract of DOI:10.1002/adsc.200900614

A series of furan-yne substrates with an arylalkynylamide substructure were prepared and subjected to catalytic amounts of phosphanegold(I) complexes. With two carbon atoms in the tether between the arylalkynylamide and the furan subunits, the formation o

Full text of DOI:10.1002/adsc.200900614

FULL PAPERS
DOI: 10.1002/adsc.200900614
Gold Catalysis: Anellated Heterocycles and Dependency of the
Reaction Pathway on the Tether Length
A. Stephen K. Hashmi,a,* Sreekumar Pankajakshan,b Matthias Rudolph,a
Elisabeth Enns,a Thomas Bander,b Frank Rominger,a and Wolfgang Freyb
a
Organisch-Chemisches Institut, Ruprecht-Karls-Universitꢀt Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg,
Germany
Fax : (+49)6221-54-4205; e-mail: hashmi@hashmi.de
Institut fꢁr Organische Chemie, Universitꢀt Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
b
Received: September 4, 2009; Published online: November 18, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900614.
Abstract: A series of furan-yne substrates with an ar- carbon atoms in the tether, the outcome was quite
ylalkynylamide substructure were prepared and sub- different, cyclopentadiene derivatives anellated to
jected to catalytic amounts of phosphanegold(I) tetrahydropyridine rings were isolated. The two dif-
complexes. With two carbon atoms in the tether be- ferent pathways suggested are supported by calcula-
tween the arylalkynylamide and the furan subunits, tions regarding the selectivity-determining step.
the formation of benzoanellated heterocycles was
observed, a number of interesting heterocyclic fram- Keywords: alkynes; arenes; benzanellation; gold;
works could be accessed in this way. With three heterocycles; homogeneous catalysis
Introduction
the distal carbon atom to a six-membered ring and
provided the new tetracyclic framework 4, again in
The importance of gold in homogeneous catalysis is fast reactions.[3] This raised our interest in the behav-
still increasing, offering a plethora of catalytic conver- iour of substrates 5 with the phenyl group on the
sions and rearrangements which lead to impressive alkyne[4] and the activating hetero
structural diversity.[1] Most of these transformations side in the tether.
are perfectly atom economic and very user-friendly as
no precautions like the exclusion of moisture or
oxygen are necessary.
ACHTUNGTRENaNGNU tom on the other
In most cases alkynes are used as substrates, but
donor-substituted alkynes like ene-ynamides also
form an interesting but little explored class of sub-
strates.[2]
Last year, we reported the gold-catalyzed synthesis
of benzoanellated heterocycles from furan substrates
with ynamides and ynol ether groups possessing the
heteroatom in the tether (Scheme 1, 1).[2f] With gold
catalysts, these substrates followed the pathway of the
normal phenol synthesis (in the case of three atoms in
the tether reacting with the proximal carbon atom to
deliver a five-membered ring in 2), but the reactions
were superior in both conversion time and selectivity.
Just recently, we investigated related substrates with
an aryl ether moiety on the other side of the alkyne
(3), leading to an inversion of the regioselectivity in
Scheme 1. Different types of alkynyl-furan substrates with
the cyclization; the alkyne now closed the ring with heteroatoms on the alkyne.
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Results and Discussion
ynamide, and the product 7f was isolated with a sig-
nificantly improved yield of 75% (entry 7). Similarly,
These substrates 5 were synthesized by Sonogashira 5g gave the benzothiophene product 7g in a yield of
coupling of the terminal ynamides 6[2f] with the corre- 74% (entry 8). An X-ray crystallographic analysis of
sponding aryl iodides (Scheme 2). The failure of the 7g proved the structure unambiguously and gave con-
Sonogashira coupling with bulky substrates (for exam- clusive support for the benzanellation chemistry
ple, 2-i-PrC6H4I), ethynyl ethers, and the failure to (Figure 1, left).[6] The substrate 5h, where the thio-
couple aryl bromides and aryl chlorides were the limi- phene moiety is connected to the alkyne at the 3-posi-
tations of this substrate synthesis.
tion, selectively at 08C (2 h) furnished 7h – a constitu-
tional isomer of 7g – in 60% yield (entry 9). The influ-
ence of the protection group is a minor one, 5i which
differs from 5h by the protection group only, gives a
quite similar result (entry 10). The substrate 5j with
two not symmetry-equivalent ortho-positions on the
arene reacted regioselectively to give the product 7j
in 53% yield (entry 11). The regioselectivity is partic-
ularly noteworthy when compared to the arylalkyne
substrates reported by Echavarren et al., where meta-
substitution of the arene produced regioisomeric mix-
tures.[7] The deactivated substrate 5k with a p-nitro
Scheme 2. Synthesis of the substrates by Sonogashira cou-
pling.
Compound 5a (R=Me, Ar=tolyl) was subjected to group on the arene, failed to react and decomposed
5 mol% of the Ph3PAuNTf2 catalyst in CD2Cl2 in an when exposed for prolonged reaction times
NMR tube and the reaction was monitored by in situ (entry 12). Compound 5l with a pyridine substitution
1H NMR spectroscopy. The conversion was slow but at the alkyne had a similar fate (entry 13). The sub-
selective, only one product was formed, and took 16 h strate 5m only underwent partial addition of water,
at 458C. Mes3PAuNTf2 showed similar activity, while the amide 8 was isolated in 18% yield (entry 14). The
with AuCl3 only decomposition of the substrate was naphthyl-substituted 5n with the brosyl (Bs) protect-
observed. Finally, a combination of Ph3PAuCl and ing group gave the phenanthrene derivative 7n in
AgBF4 (5 mol%, 1:1) was found to catalyze the reac- 72% yield (entry 15). The substrate 5o, with a benzo-
tion much faster (complete conversion in 4 h at room furan group on the alkyne and an ethyl group on C-5
temperature in CD2Cl2). Control experiments with of the furan reacted beautifully to give the dibenzo-
AgBF4 and with trifluoroacetic acid gave no conver- furan derivative 7o in 76% yield (entry 16). So did
sion while trifluoromethanesulfonic acid decomposed the substrate 5p with an N-methylindole moiety and
the substrate.
the benzoindole product was isolated in 41% yield
Characterization of the purified product showed it (entry 17). A substrate with a bulky substituent like
to be the benzanellated dihydroindole derivative 7a phenanthrene on the alkyne (5q) was also converted
(Table 1, entry 1, 53% yield). Particularly pleasing – albeit slower – and the triphenylene derivative 7q
was the observation that the enol ether part of the was isolated in 43% yield (entry 18). We also exam-
furan moiety was eliminated from the central six- ined the reactivity of unsubstituted furan substrate 5r,
membered ring (as an enol then equilibrating to the but the system was too passive to react (entry 19).
1
more stable ketone), establishing the synthetically im- Typical H NMR shifts indicating a successful conver-
portant anellated arene unit. Scope and reactivity of sion are the two triplets of the N-tosylpyrrolidine sub-
further substrates were explored (Table 1, 5b–5x).
structure, appearing around 2.79–3.06 ppm and 3.98–
The substrate 5b with a more electron-donating me- 4.06 ppm with a coupling constant of 8.2 Hz, as well
thoxy group initially was reacted at slightly higher as the methylene group in the side chain (between
temperature (458C) in only 1 h to furnish the product the carbonyl group and the arene) as a characteristic
7b in 57% yield (entry 2), but also delivered 7b in singlet at 3.63–4.01 ppm (only with further anellated
3.5 h at room temperature in quite similar yield arenes in 7o and 7q this signal appears at 4.10 ppm
(entry 3). The naphthyl-substituted 5c furnished the and 4.23 ppm, respectively).
tetracyclic compound 7c in 53% yield with a reaction
Having established the generality of arene nucleo-
time of 7 h at room temperature (entry 4). The sub- philes, the substrate 5s with a hydroxy group as a po-
strate 5d with a heteroaryl group attached to the tential nucleophile was subjected to the catalyst. But
alkyne gave the benzofuran derivative 7d in an excel- then only the formation of the Meyer–Schuster-type
lent yield of 79% after 6 h at room temperature a,b-unsaturated amide 9 was observed (Scheme 3).
(entry 5). Even thiophene 5e also led to the benzo-
thiophene product 7e in 65% yield (entry 6).[5] We one additional carbon atom in the tether had a com-
then switched to 5f, brosyl (Bs)-substituted pletely different outcome. With 5t selectively a new
The gold-catalyzed conversion of arylynamides with
a
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Table 1. Gold-catalyzed reaction of arylynamides 5a–5r (two-carbon tether).
Entry
Substrate 5
Time [h] Temperature [oC]
Product
Yield [%]
53
1[a]
5a
4
r.t.
7a
2[b]
5b
5b
1
45
7b
7b
57
54
3[b]
3.5
r.t.
4[a]
5c
7
r.t.
7c
53
5[a]
6[a]
7[a]
5d
5e
5f
6
1
4
r.t.
r.t.
r.t.
7d
7e
7f
79
65
75
8[a]
5g
3
r.t.
7g
74
9[a]
5h
5i
2
1
1
0
7h
7i
60
66
53
10[a]
r.t.
50
11[a]
5j
7j
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Table 1. (Continued)
Entry
Substrate 5
Time [h] Temperature [oC]
Product
Yield [%]
-
12[b]
5k
5l
24
20
50
65
substrate decomposes
13[b]
no reaction
-
14[a]
5m
5n
1
8
r.t.
r.t.
8
18
15[a]
7n
72
16[a]
5o
5p
3
r.t.
r.t.
7o
7p
76
41
17[a]
12
18[a]
5q
5r
20
48
45
45
7q
43
19[a]
no reaction
[a]
In CH2Cl2.
In CHCl3.
[b]
product was formed. Again the control experiments volved. The substrate 5u with a p-tolyl substitution on
with AgBF4 or trifluoroacetic acid gave no conver- the alkyne followed and a similar reaction, product
sion, trifluoromethanesulfonic acid led to an unspecif- 10u was isolated in 52% yield (entry 2). We have
ic decomposition of the substrate.
managed to obtain an X-ray structure analysis of this
The 1D and 2D NMR spectra combined with mass compound, thereby unambiguously proving the prod-
spectroscopic data led to the assumption that the uct identity (Figure 1, right).[6]
product would be 10t, a cyclic unsaturated ketone
A heteroaryl ynamide substrate 5v also furnished
with a stereogenic centre (Table 2, entry 1). The reac- the cyclopentenone derivative 10v in 50% yield
tion was much faster (finished in 45 min at room tem- (entry 3). An electron-withdrawing group on the
perature) and no trace of the benzanellated product alkyne was not tolerated and hence the pyridinyl sub-
7t was detected in the reaction mixture. This indicates stituted 5w remained unreactive (entry 4). Typical
that a completely different mechanistic pathway is in- 1H NMR shifts for the products 10 are the resonance
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Figure 1. Solid state molecular structure of the benzanellated product 7g (left) and the cyclopentenone product 10u (right).
of the acetyl group (CH3CO) at the cyclopentadiene, group of the cyclopentadiene ring, a doublet with a
a singlet at 2.19–2.23 ppm, and the vinylic methine coupling constant of 1.3–1.5 Hz at 7.11–7.12 Hz.
Table 2. Gold-catalyzed conversion of arylynamides 5s–5w (three-carbon tether).[a]
Entry
Substrate 5
Time [h]
Temperature [oC]
Product
Yield [%]
56
1
5t
0.7
r.t.
10t
2
5u
1
r.t.
10u
52
3
4
5v
4
r.t.
50
10v
50
–
5w
20
no reaction
5
5x
1.5
r.t.
complex mixture
–
[a]
All the reactions were done in CH2Cl2.
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Scheme 3. Gold-catalyzed conversion of 5s.
Scheme 4. Gold-catalyzed conversion of methylynamide 5y.
The substrate 5x yielded a complicated mixture of
products (entry 5). The NMR spectra of the crude re-
action mixture showed the presence of both cyclopen-
tenone and benzanellated products, as identified in
the mixture by the characteristic signals mentioned
for products 7 and 10 above, but these could not be
separated.
Compared to the known gold-catalyzed reactions of
arylalkynes,[7] which did not always react selectively,
the arylalkynylamides due to the directing properties
of the amide group showed improved selectivities.
We also investigated if an alkyl group attached to
the alkyne would lead to similar transformations but
the substrate 5y underwent water addition to form
the amide 11, in 25% yield (Scheme 4).
Scheme 5. Proposed mechanism for the gold-catalyzed benz-
AHCTUNGTERGaNNUN nnelation of arylynamides 2.
The mechanistic pathway for the formation of ben-
zanellated products 7 from arylynamides 5a–5p seems reaction (to J), and this lack of reactivity is consid-
straightforward and proceeds through the classical ered to be the main reason behind the failure of gold/
exo-1,6-enyne cyclization mode[8] (Scheme 5). The ac- platinum-catalyzed phenol synthesis from terminally
tivation of the alkyne by gold leads to the formation substituted furyl alkynes. The proposed intermediate I
of intermediates A or B having a cationic or carbene might undergo electrocyclization to the heteroatom-
identity,[9] respectively. A Friedel–Crafts type[10] elec- stabilized intermediate K followed by elimination to
trophilic attack (C) followed by rearomatization of form the cyclopentenone compound L, which eventu-
the arene unit leads to the cyclized intermediate D. ally is transformed to the final product 10 by a 1,5-H
This intermediate could protodeaurate (E), then un- shift, this sequence I/K/L resembles the mechanism of
dergo the crucial second aromatization process by the gold-catalyszd synthesis of acylindenes, which
elimination of the furyl enol ether bridge to deliver shows a similar electrocyclization/elimination/1,5-H
the final product 7.
shift sequence.[12] The activity of the intermediate I,
The mechanistic route for the cyclopentenone compared to its analogue in phenol synthesis is attrib-
structures 10 from arylynamides 5s–5x with the longer uted to the presence of the heteroatom (nitrogen
tether is shown in Scheme 6. The reaction is initiated here) which would assist to stabilize the formation of
by 6-exo-dig attack to give the cation F or carbene G charges in the allylic cation K, but not in the penta-
intermediate. Ring-opening forms the conjugated dienyl cation I. The absence of benzanellation path-
monocyclic intermediate I. Species I resembles the way possibly goes back to a different conformation
crucial carbene intermediate in gold- and platinum- caused by the different length of the tether in raising
catalyzed phenol synthesis from furyl alkynes (the the distance of the arene moiety and the electrophilic
latter differs from I only by lack of the aryl C-3 of the furan unit (comparing the five-membered
group).[4,11] Such an intermediate was reported[4] to be ring in A and the six-membered ring in F). The as-
incapable (due to the presence of the arene moiety sumption is supported by the fact that the substrate
on the carbene/carbocation substructure) of further 5x with a naphthyl moiety (offering a second aromatic
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Gold Catalysis: Anellated Heterocycles and Dependency of the Reaction Pathway
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Scheme 6. Proposed mechanism for the formation of cyclopentenones from gold catalysis of arylynamides 2 with three-
carbon tether.
ring which still can be reached by C-3 of the furan) carbon-tether, the electrophilic carbon of the furan
was found to show signals of both types of products ring could attack the phenyl group and deliver an in-
1
(7 and 10) in the H NMR of the crude product as dis- termediate C and H. But calculating the correspond-
cussed above.
ing s-complexes after the attack at the benzene ring
In order to evaluate the feasibility of the mechanis- reveals the difference, C is a stable intermediate,
tic pathways, we conducted DFT calculations includ- while H does turn out not to be a stable structure. We
ing zero point corrections of selected key intermedi- could only find a local minimum (45.0 kJmolÀ1 higher
À
ates. First we calculated the intermediates A and F than F1) in which a C C interaction starts to form
from Scheme 5 and Scheme 6, which are the inter- (1.65 ꢃ), but due to the geometrical restraints in the
mediates before the selectivity-determining step. They molecule cannot form a stable bond. On the other
are depicted in Figure 2. There is no evidence for a hand the open-chained intermediate I is a minimum
major contribution of the cyclopropyl-forms B and G. energetically only 26.0 kJmolÀ1 higher than F1. The
For both A and F we found two different conformers calculation also shows the additional conjugative sta-
A1/A2 and F1/F2. All these conformers are local bilization of the cation in intermediate I by the
minima, interestingly for both A and F the thermody- phenyl group, part of the explanation for not seeing
namically more stable conformer is the one with a the cyclization to J.
shorter distance between the potentially reacting cen-
ters (details of the calculations in the Supporting In-
formation). A1 has a carbon-carbon distance between Conclusions
the reacting centers of 3.08 ꢃ, A2 is 8.8 kJmolÀ1
higher in energy and shows a much bigger distance of Over all, we have explored gold-catalyzed reactions
3.64 ꢃ. The corresponding value for F1 is 2.99 ꢃ, F2 of furanyne substrates with an aryl group on the distal
is 20.6 kJmolÀ1 higher in energy with a distance of end of the triple bond and an amide group on the
3.87 ꢃ. This would indicate that in both intermediates, proximal end for the first time. The outcome of the
A1 for the two-carbon-tether and F1 for the three- reaction selectively depends on the length of the
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Figure 2. Molecular geometries for key intermediates obtained from DFT calculations.
slowly added to 8M HCl (1.6 equiv.) and was stirred for
1.5 h at room temperature. The organic part was extracted
with dichloromethane and then dried over MgSO4. Column
chromatography (silica gel, petroleum ether:ethyl acetate)
furnished the nitroalkene product as yellow crystals; yield:
144 mg (84%). Rf (petroleum ether:ethyl acetate, 1:1)=
tether, in the case of three atoms in the tether be-
tween the furan and the alkyne, anellated systems
composing of the aryl group, a new benzene ring with
a side chain and a five-membered nitrogen heterocy-
cle are formed. In the case of four atoms in the
tether, acylcyclopentadienes anellated to a six-mem-
bered nitrogen heterocycle are isolated. Both ob-
served routes open new possibilities for the synthesis
of important anellated arenes and anellated heteroar-
enes under very mild reaction conditions. The keto
group present at the beta-carbon atom of the side-
chain of the products 7 will allow a wide spectrum of
further functionalizations.
˜
0.44; IR (neat): n=3129, 2992, 2919, 1670, 1552, 1520, 1498,
1070, 970, 826, 821, 725, 558 cmÀ1 1H NMR (250 MHz,
;
CDCl3): d=1.28 (t, J=7.6 Hz, 3H), 2.65 (q, J=7.6 Hz, 2H),
6.24 (d, J=3.5 Hz, 1H), 6.82 (d, J=3.5 Hz, 1H), 7.44 (d, J=
13.2 Hz, 1H), 7.72 (d, J=13.2 Hz, 1H); 13C NMR
(62.9 MHz, CDCl3): d=11.74 (q), 21.81 (t), 108.7 (d), 122.0
(d), 125.6 (d), 133.3 (d), 145.1 (s), 163.8 (s); MS (EI): m/z
(%)=167 (100) (M+), 138 (35), 124 (60), 105 (76), 83 (60),
77 (40), 55 (30); anal. calcd. for C8H9NO3: C 57.48, H 5.43,
N 8.38; found: C 57.70, H 5.49, N 8.27.
Experimental Section
2-(5-Ethylfuran-2-yl)ethylamine
2-Ethyl-5-(2-nitrovinyl)furan[13]
3.00 g (18.0 mmol, 1 equiv.) of 1 were dissolved in 50 mL of
anhydrous ether. The solution was slowly added to 2.00 g
(54.0 mmol, 3 equiv.) of LiAlH4 in 150 mL of anhydrous
ether under nitrogen at 08C. The reaction mixture was
stirred for 1 h at room temperature and then refluxed for
18 h. After cooling to 08C, the reaction was quenched with
10 mL of NH4Cl. The solid was filtered off and the organic
124 mg (1 mmol, 1 equiv.) of 5-ethylfurfural were added to
an ice-cold solution of 1 mL methanol and 0.13 mL of nitro-
methane (2 mmol, 2 equiv.). Aqueous 1M NaOH
(2.5 equiv.) was added followed by 4 mL of ice/water. The
reaction mixture was stirred for 20 min at 08C and then
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Gold Catalysis: Anellated Heterocycles and Dependency of the Reaction Pathway
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layer was extracted with ether, the combined organic phases
dried over MgSO4. Column chromatography (silica gel, pe-
troleum ether:ethyl acetate:1% NEt3) furnished the pure
amine as a light brown oil; yield: 1.52 g (64%); Rf (petro-
mixture was warmed to room temperature for 36 h. The sol-
vent was removed under vacuum and the crude product was
passed through a pad of silica gel to remove all residual im-
purities. The crude TMS-protected alkyne obtained as
brownish-yellow oil (yield: 2.80 g, 7.20 mmol) was dissolved
in 20 mL of methanol and 1.26 g (9.00 mmol, 1.2 equiv.) of
K2CO3 were added in portions. The suspension was stirred
at room temperature for 1 h after which the solvent was re-
moved and column chromatography done (silica gel, petro-
leum ether:ethyl acetate). The pure product was isolated as
a yellow oil; overall yield: 1.20 g (42%); Rf (petroleum
˜
leum ether:ethyl acetate, 1:1)=0.05; IR (film): n=2970,
1
2937, 1566, 1464, 1325, 1211, 1011, 934, 777 cmÀ1; H NMR
(300 MHz, CDCl3): d=1.21 (t, J=8.0 Hz, 3H) 1.43 (bs, 1H),
2.60 (q, J=8.0 Hz, 2H), 2.72 (t, J=6.8 Hz, 2H), 2.94 (t, J=
7.24 Hz, 2H), 5.86 (d, J=3.2 Hz, 1H), 5.93 (d, J=3.2 Hz,
1H); 13C NMR (75.5 MHz, CDCl3): d=12.13 (q), 21.34 (t),
32.50 (t), 40.83 (t), 104.2 (t), 106.3 (t), 151.9 (s), 156.5 (s);
MS (EI): m/z (%)=140 (10) (M+1), 123 (100); HR-MS
(ESI): m/z=140.1070, calcd. for C8H13NO: 140.1079.
˜
ether:ethyl acetate, 4:1)=0.50; IR (film): n=3296, 2972,
2936, 2135, 1698, 1596, 1566, 1453, 1362, 1166, 1090, 950,
683 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=1.19 (t, J=
7.6 Hz, 3H), 2.44 (s, 3H), 2.57 (q, J=7.6 Hz, 2H), 2.75 (s,
1H), 2.92 (t, J=7.5 Hz, 2H), 3.58 (t, J=7.6 Hz, 2H), 5.81–
5.84 (m, 1H), 5.92 (d, J=3.1 Hz, 1H), 7.33 (d, J=8.3 Hz,
2H), 7.78 (d, J=8.3 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz):
d=12.14 (q), 21.29 (t), 21.67 (q), 26.99 (t), 49.78 (t), 59.48
(d), 75.66 (s), 104.4 (d), 107.3 (d), 127.6 (d, 2C), 129.8 (d,
2C), 134.5 (s), 144.7 (s), 149.0 (s), 156.9 (s); MS (APCI):
m/z (%)=318 (100) (M+1)+, 123 (24); HR-MS (APCI):
m/z=317.1079, calcd. for C17H19NO3S: 317.1086.
2-(5-Ethylfuran-2-yl)-N-tosylethanamine
1.30 g (9.40 mmol, 1 equiv.) of the amine 2 were dissolved in
20 mL of dichloromethane. 1.4 mL (10.4 mmol, 1.1 equiv.) of
triethylamine and 1.80 g (9.40 mmol, 1 equiv.) of tosyl chlo-
ride were added to this solution. The reaction mixture was
stirred at room temperature for 24 h.The reaction was
quenched with 10 mL of water, and the organic layer was
extracted with dichloromethane. After drying over MgSO4,
column chromatography (silica gel, petroleum ether:ethyl
acetate) gave the product as a yellow oil; yield: 1.87 g
(70%); Rf (petroleum ether:ethyl acetate, 4:1)=0.30; IR
4-Bromo-N-[2-(5-methyl-furan-2-yl)-
ethyl]benzenesulfonamide
˜
(film): n=3282, 2971, 2937, 1566, 1420, 1322, 1153, 1092,
1
1009, 795, 660, 549 cmÀ1; H NMR (300 MHz, CDCl3): d=
1.17 (t, J=7.3 Hz, 3H), 2.41 (s, 3H), 2.53 (q, J=8.0 Hz,
2H), 2.71 (t, J=7.0 Hz, 2H), 3.20 (q, J=6.8 Hz, 2H), 4.71
(t, J=6.9 Hz , 1H), 5.82 (d, J=3.2 Hz, 1H), 5.88 (d, J=
3.2 Hz, 1H), 7.30 (d, J=8.1 Hz, 2H), 7.71 (d, J=8.1 Hz,
2H); 13C NMR (75.5 MHz, CDCl3): d=12.09 (q), 21.30 (t),
21.54 (q), 28.31(t), 41.77 (t), 104.4 (d), 107.4 (d), 127.1 (d,
2C), 129.7 (d, 2C), 136.9 (s), 143.4 (s), 149.7 (s), 157.1 (s);
MS (EI): m/z (%)=293 (40) (M+), 184 (30), 155 (95), 122
(70), 109 (100), 91 (60); anal. calcd. for C15H19NSO3: C
61.41, H 6.53, N 4.77; found: C 61.35, H 6.55, N 4.92.
1.30 g (9.40 mmol, 1 equiv.) of 2-(5-methylfuran-2-yl)ethyl-
AHCTUNGTRENNUNG
amine[15] were dissolved in 20 mL of dichloromethane.
Cooled to 08C and 1.40 mL (10.4 mmol, 1.1 equiv.) of trie-
thylamine, pinch of DMAP and 2.60 g (10.3 mmol,
a
1.1 equiv.) of brosyl chloride were added to this solution.
The reaction mixture was stirred at toom temperature for
12 h.The reaction was quenched with 10 mL of water, and
the organic layer was extracted with dichloromethane and
the extract dried over MgSO4. Column chromatography
(silica gel, petroleum ether:ethyl acetate) gave the product
as a pale-yellow solid; yield: 2.60 g (72%); mp: 56–588C; Rf
N-[2-(5-Ethylfuran-2-yl)-ethyl]-N-ethynyl-4-
˜
(petroleum ether:ethyl acetate, 1:1)=0.45; IR (film): n=
methylbenzenesulfonamide[14]
3275, 2918, 1573, 1471, 1388, 1320, 1155, 1065, 1009, 927,
821, 783, 738, 655, 602 cmÀ1 1H NMR (CDCl3, 250 MHz):
;
d=2.20 (s, 3H), 2.73 (t, J=6.5 Hz, 2H), 3.23 (q, J=6.4 Hz,
2H), 4.61 (t, J=6.3 Hz, 1H), 5.80–5.84 (m, 1H), 5.88 (d, J=
3.0 Hz, 1H), 7.59–7.72 (m, 4H); 13C NMR (CDCl3,
62.9 MHz): d=13.49 (q), 28.30 (t), 41.79 (t), 106.1 (d),
(107.9 (d), 127.6 (s), 128.6 (d, 2C), 132.3 (d, 2C), 139.0 (s),
149.5 (s), 151.5 (s); MS (APCI): m/z (%)=344 (7) (M+1),
109 (100); HR-MS (APCI): m/z=342.9876, calcd. for
C13H14BrNO3S: 342.9878; anal. calcd. for C13H14BrNO3S: C
45.36, H 4.10, N 4.07; found: C 45.49, H 4.13, N 4.04.
2.65 g (9.00 mmol, 1 equiv.) of the amine 3 were dissolved in
70 mL of dry toluene under nitrogen. The solution was
cooled to 08C and 4.00 mL (10 mmol, 1.1 equiv.) n-butyl-
lithium (2.5M solution in hexane) were added drop by drop.
The reaction mixture was stirred for 1 h at the same temper-
ature. 4.90 g (10.8 mmol, 1.2 equiv.) of trimethylsilylethynyl-
4-Bromo-N-ethynyl-N-[2-(5-methyl-furan-2-
yl)ethyl]benzenesulfonamide
4.00 g (11.6 mmol, 1 equiv.) of amine 5 were dissolved in
A
100 mL of dry toluene under nitrogen. The solution was
Adv. Synth. Catal. 2009, 351, 2855 – 2875
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asc.wiley-vch.de
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A. Stephen K. Hashmi et al.
FULL PAPERS
722, 649 cmÀ1
;
1H NMR (CD2Cl2, 250 MHz): d=2.20 (s,
cooled to 08C and n-butyllithium was added drop by drop.
The reaction mixture was stirred for 1 h at the same temper-
ature. 6.20 g (13.8 mol, 1.2 equiv.) of trimethylsilylethynylio-
donium triflate were added in portions and the reaction
mixture was warmed to room temperature for 36 h. The sol-
vent was removed under vacuum and the product was
passed through a short pad of silica gel. The crude TMS-
protected alkyne thus obtained (yield: 4.00 g, 9.00 mmol)
was dissolved in 20 mL of methanol and 1.50 g (10.8 mmol,
1.2 equiv.) of K2CO3 were added in portions. The suspension
was stirred at room temperature for 1 h after which the sol-
vent was removed and column chromatography done (silica
gel, petroleum ether:ethyl acetate). The pure product was
isolated as a colourless solid; overall yield: 2.80 g (65%);
mp: 70–728C; Rf (petroleum ether:ethyl acetate, 4:1)=0.53;
3H), 2.34 (s, 3H), 2.44 (s, 3H), 2.96 (t, J=7.6 Hz, 2H), 3.65
(t, J=7.6 Hz, 2H), 5.83–5.85 (m, 1H), 5.94 (d, J=3.2 Hz,
1H), 7.10 (dd, J=8.6 Hz, 0.7 Hz, 2H), 7.27 (d, J=8.2 Hz,
2H), 7.33 (dd, J=8.6 Hz, 0.7 Hz, 2H), 7.81 (d, J=8.3 Hz,
2H); 13C NMR (CDCl3, 62.9 MHz): d=13.47 (q), 21.45 (q),
21.65 (q), 27.18 (t), 50.22 (t), 70.94 (s), 81.18 (s), 106.1 (d),
107.5 (d), 119.6 (s), 127.6 (d, 2C), 127.8 (d, 2C), 129.7 (d,
2C), 131.5 (d, 2C), 134.6 (s), 138.0 (s), 144.5 (s), 149.3 (s),
151.2 (s); MS (EI+): m/z (%)=394 (M+1)+ (14), 393 (M+)
(41), 246 (55), 214 (57), 108 (96), 91 (100); HR-MS (ESI+):
m/z=394.1396, calcd. for C23H23NO3S: 393.1399.
N-(4-Methoxyphenylethynyl)-4-methyl-N-[2-(5-
methyl-furan-2-yl)ethyl]benzenesulfonamide (5b)
˜
IR (film): n=3296, 2137, 1573, 1367, 1169, 1068, 965, 785,
1
744, 664 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.20 (s, 3H),
2.78 (s, 1H), 2.92 (t, J=7.5 Hz, 2H), 3.60 (t, J=7.5 Hz, 2H),
5.79–5.82 (m, 1H), 5.90 (d, J=3.1 Hz, 1H), 7.64–7.76 (m,
4H); 13C NMR (CDCl3, 75.5 MHz): d=13.59 (q), 26.97 (t),
49.96 (t), 60.00 (d), 75.02 (s), 106.1 (d), 107.7 (d), 128.9 (d,
2C), 132.5 (d, 2 C), 136.4 (s), 148.8 (s), 151.2 (s), 161.1 (s);
MS (ESI+): m/z (%)=390 (100) (M+Na)+, 368 (M+1)+,
186 (16); HR-MS (ESI+): m/z=366.9885, calcd. for
C15H14BrNO3S: 366.9878.
Yield: 31%, brown oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.42; IR (film): n=2923, 2235, 1605, 1511, 1363, 1247,
1
1167, 904, 721 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.20 (s,
3H), 2.45 (s, 3H), 2.96 (t, J=7.8 Hz, 2H), 3.65 (t, J=7.8 Hz,
2H), 3.81 (s, 3H), 5.81–5.83 (m, 1H), 5.92 (d, J=3.2 Hz,
1H), 6.8 (d, J=8.8 Hz, 2H), 7.29–7.35 (m, 4H), 7.81 (d, J=
8.4 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz): d=13.59 (q),
21.71 (q), 27.28 (t), 29.48 (q); 50.40 (t), 55.35 (q), 70.71 (s),
80.5 (s), 106.1 (d), 107.5 (d), 113.8 (d, 2C), 114.7 (s), 127.6
(d, 2C), 129.6 (d, 2C), 133.4 (d, 2C), 144.5 (s), 149.4 (s),
151.1 (s), 159.6 (s); MS (ESI+): m/z (%)=432 (100) (M+
Na)+; HR-MS (EI+): m/z=409.1349, calcd. for C23H23NO4S:
409.1348.
General Procedure for the Sonogashira Couplings
4-Methyl-N-[2-(5-methylfuran-2-yl)ethyl]-N-
1.00 mmol (1 equiv.) of the ynamide[16] and 1.10 mmol of the naphthalen-1-ylethynylbenzenesulfonamide (5c)
aryl iodide were added to a mixture of 2 mL dry toluene
and 2 mL triethylamine. 5 mol% of tetrakis(triphenylphos-
phine)palladium(0) was added and the mixture was de-
gassed. After being stirred for 10 min at room temperature
1.5 mol% copper(I) iodide was added. The reaction mixture
was heated at 608C for 2 h. The solvent was removed under
vacuum and the crude product was purified over flash
column chromatography (silica gel, petroleum ether/ethyl
acetate).
Yield: 29%, yellow oil; Rf (petroleum ether:ethyl acetate,
4-Methyl-N-[2-(5-methylfuran-2-yl)ethyl]-N-p-
˜
4:1)=0.33; IR (film): n=3057, 2921, 2230, 1364, 1167,
tolylethynylbenzenesulfonamide (5a)
1090 cmÀ1 1H NMR (CDCl3, 300 MHz): d=2.20 (s, 3H),
;
2.44 (s, 3H), 3.06 (t, J=7.6 Hz, 2H), 3.78 (t, J=7.6 Hz, 2H),
5.82–5.85 (m, 1H), 5.96 (d, J=3.1 Hz, 1H), 7.33 (d, J=
Yield: 31%, pale brown oil, Rf (petroleum ether:ethyl ace-
˜
tate, 4:1)=0.44; IR (film): n=2922, 2235, 1365, 1168, 903,
2864
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ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 2855 – 2875

Gold Catalysis: Anellated Heterocycles and Dependency of the Reaction Pathway
FULL PAPERS
8.3 Hz, 2H), 7.38–7.42 (m, 1H), 7.50–7.58 (m, 3H), 7.79 (d,
J=8.3 Hz, 2H), 7.86 (d, J=8.4 Hz, 2H), 8.18–8.22 (m, 1H);
13C NMR (CDCl3, 75.5 MHz): d=13.54 (q), 21.74 (q), 27.31
(t), 50.37 (t), 69.5 (s), 86.6 (s), 106.2 (d), 107.6 (d), 120.5 (s),
125.1 (d), 126.2 (d), 126.3 (d), 126.7 (d), 127.7 (d, 2C), 128.2
(d), 129.7 (d), 129.8 (d, 2C), 130.9 (d), 133.1 (s), 133.2 (s),
134.7 (s), 144.7 (s), 149.2 (s), 151.2 (s); MS (ESI+): m/z
(%)=452 (100) (M+Na)+; HR-MS (ESI+): m/z=430.1479,
C26H23NO3S: calcd: 430.1469.
4-Bromo-N-(4-methoxyphenylethynyl)-N-[2-(5-
methylfuran-2-yl)ethyl]benzenesulfonamide (5f)
Yield: 17%, yellow oil; Rf (petroleum ether:ethyl acetate,
4-Methyl-N-[2-(5-methylfuran-2-yl)ethyl]-N-(5-
methylfuran-2-ylethynyl)benzenesulfonamide (5d)
˜
4:1)=0.35; IR (film): n=2925, 1605, 1573, 1367, 1248, 1170,
1
902, 725, 649 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.21 (s,
3H), 2.96 (t, J=7.4 Hz, 2H), 3.67 (t, J=7.5 Hz, 2H), 3.81 (s,
3H), 5.80–5.83 (m, 1H), 5.92 (d, J=3.1 Hz, 1H), 6.83 (d, J=
8.8 Hz, 2H), 7.31 (d, J=8.9 Hz, 2H), 7.67 (d, J=8.6 Hz,
2H), 7.76 (d, J=8.6 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz):
d=13.57 (q), 27.15 (t), 50.46 (t), 55.40 (q), 71.03 (s), 79.78
(s), 106.1 (d), 107.7 (d), 114.0 (d, 2C), 114.3 (s), 128.7 (s),
129.0 (d, 2C), 132.3 (d, 2C), 133.6 (d, 2C), 136.6 (s), 149.2
(s), 151.3 (s), 159.7 (s); MS (ESI): m/z (%)=473 (3) (M+),
255 (100), 212 (42); HR-MS (ESI): m/z=474.0375, calcd. for
C22H20BrNO4S: 474.0371.
Yield: 20%, yellow oil; Rf (petroleum ether:ethyl acetate,
˜
8:1)=0.25; IR (film): n=2922, 2220, 1543, 1436, 1365, 1264,
1167, 1090, 1019, 920, 786, 712 cmÀ1 1H NMR (CD2Cl2,
;
300 MHz): d=2.20 (s, 3H), 2.29 (s, 3H), 2.44 (s, 3H), 2.94
(t, J=7.8 Hz, 2H), 3.65 (t, J=7.9 Hz, 2H), 5.79–5.82 (m,
1H), 5.91 (d, J=5.9 Hz, 1H), 5.96–5.99 (m, 1H), 6.51 (d, J=
3.2 Hz, 1H), 7.33 (d, J=8.2 Hz, 2H), 7.79 (d, J=8.2 Hz,
2H); 13C NMR (CDCl3, 75.5 MHz): d=13.46 (q), 13.95 (q),
21.70 (q), 27.18 (t), 50.36 (t), 62.41 (s), 85.78 (s), 106.1 (d),
107.3 (d), 107.6 (d), 118.8 (d), 127.6 (d, 2C), 129.8 (d, 2C),
134.8 (s), 134.9 (s), 144.7 (s), 149.2 (s), 151.2 (s), 154.2 (s);
MS (ESI+): m/z (%)=406 (72) (M+Na)+, 301 (100); HR-
MS (ESI): m/z=406.1078, calcd. for C21H21NO4S: 406.1088.
4-Bromo-N-[2-(5-methylfuran-2-yl)ethyl]-N-thiophen-
2-ylethynylbenzenesulfonamide (5g)
4-Methyl-N-[2-(5-methylfuran-2-yl)ethyl]-N-thiophen-
2-ylethynylbenzenesulfonamide (5e)
Yield: 36%, yellow oil; Rf (petroleum ether:ethyl acetate,
˜
8:1)=0.50; IR (film): n=3102, 2920, 2226, 1572, 1368, 1168,
1
1088, 1067, 783, 742, 703, 592, 565 cmÀ1; H NMR (CDCl3,
300 MHz): d=2.20 (s, 3H), 2.95 (t, J=7.4 Hz, 2H), 3.69 (t,
J=7.4 Hz, 2H), 5.80–5.83 (m, 1H), 5.91 (d, J=3.2 Hz, 1H),
6.96–7.00 (m, 1H), 7.18 (dd, J=3.8 Hz, 1.3 Hz, 1H), 7.29
(dd, J=5.2 Hz, 1.2 Hz, 1H), 7.65–7–78 (m, 4H); 13C NMR
(CDCl3, 75.46 MHz): d=13.49 (q), 27.16 (t), 50.51 (t), 64.68
(s), 84.82 (s), 106.1 (d), 106.8 (d), 122.4 (s), 127.0 (d), 128.1
(d), 128.9 (s), 129.0 (d, 2C), 132.4 (d, 2C), 133.4 (d), 136.4
(s), 148.9 (s), 151.2 (s); MS (ESI+): m/z (%)=471 (100)
(M+Na)+, 231 (59); HR-MS (ESI): m/z=448.9746, calcd.
for C19H16BrNO3S2: 448.9750.
Yield: 41%, yellow oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.26; IR (film): n=2922, 2227, 1366, 1167, 1090, 709,
1
662, 547 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.20 (s, 3H),
2.45 (s, 3H), 2.94 (t, J=7.6 Hz, 2H), 3.67 (t, J=7.6 Hz, 2H),
5.81–5.83 (m, 1H), 5.92 (d, J=3.2 Hz, 1H), 6.95–6.98 (m,
1H), 7.17 (dd, J=3.7 Hz, 1.1 Hz, 1H), 7.26–7.28 (m, 1H),
7.35 (d, J=8.3 Hz, 2H), 7.80 (d, J=8.4 Hz, 2H); 13C NMR
(CDCl3, 75.5 MHz): d=13.47 (q), 21.69 (q), 27.26 (t), 50.35
(t), 64.24 (s), 85.46 (s), 106.1 (d), 107.6 (d), 122.8 (s), 127.0
(d), 127.6 (d, 2C), 127.8 (d), 129.8 (d, 2C), 133.1 (d), 134.5
(s), 144.7 (s), 149.2 (s), 151.1(s); MS (EI+): m/z (%)=386
(52) (M+H)+, 231 (100); HR-MS (ESI+): m/z= 386.0879,
calcd. for C20H19NO3S2: 386.0886.
4-Bromo-N-[2-(5-methylfuran-2-yl)ethyl]-N-thiophen-
2-ylethynylbenzenesulfonamide (5h)
Yield: 27%, brown oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.62; IR (film): n=3106, 2920, 2238, 1572, 1367, 1169,
1068, 901, 863, 782, 744, 592, 569 cmÀ1 1H NMR (CDCl3,
;
300 MHz): d=2.20 (s, 3H), 2.98 (t, J=7.4 Hz, 2H), 3.68 (t,
J=7.4 Hz, 2H), 5.81–5.83 (m, 1H), 5.92 (d, J=3.1 Hz, 1H),
7.05 (dd, J=5.0 Hz, 1.0 Hz, 1H), 7.25–7.29 (m, 1H), 7.41
(dd, J=3.0 Hz, 1.1 Hz, 1H), 7.68 (d, J=8.7 Hz, 2H), 7.76 (d,
Adv. Synth. Catal. 2009, 351, 2855 – 2875
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asc.wiley-vch.de
2865

A. Stephen K. Hashmi et al.
FULL PAPERS
(s), 159.3 (s); MS (ESI+): m/z (%)=432 (100) (M+Na)+;
HR-MS (EI+): m/z=409.1348, calcd. for C23H23NO4S:
409.1345.
4-Methyl-N-[2-(5-methylfuran-2-yl)ethyl]-N-(4-
nitrophenylethynyl)benzenesulfonamide (5k)
J=8.7 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz): d=13.54 (q),
27.17 (t), 50.38 (t), 66.30 (s), 80.58 (s), 106.1 (d), 107.7 (d),
121.1 (s), 125.3(d), 128.8 (s), 129.0 (d, 2C), 129.3 (d), 130.3
(d), 132.5 (d, 2C), 136.6 (s), 149.0 (s), 151.3 (s); MS (APCI):
m/z (%)=451 (100) (M+H)+, 450 (98) (M+), 231 (99); HR-
MS (APCI): m/z=449.9845, calcd. for C19H16BrNO3S2:
448.9879.
Yield: 43%, brown oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.41; IR (film): n=2923, 2225, 1593, 1514, 1368, 1337,
4-Methyl-N-[2-(5-methyl-furan-2-yl)ethyl]-N-
thiophen-3-ylethynyl-benzenesulfonamide (5i)
1
1167, 1090, 852, 748, 685 cmÀ1; H NMR (CDCl3, 300 MHz):
d=2.20 (s, 3H), 2.42 (s, 3H), 2.97 (t, J=7.5 Hz, 2H), 3.72 (t,
J=7.5 Hz, 2H), 5.82–5.85 (m, 1H), 5.92 (d, J=3.2 Hz, 1H),
7.36 (d, J=8.4 Hz, 2H), 7.43 (d, J=8.8 Hz, 2H), 7.81 (d, J=
8.3 Hz, 2H), 8.16 (d, J=8.8 Hz, 2H); 13C NMR (CDCl3,
75.5 MHz): d=13.53 (q), 21.75 (q), 27.41 (t), 50.27 (t), 70.79
(s), 88.60 (s), 106.2 (d), 107.8 (d), 123.6 (d, 2C), 127.7 (d,
2C), 129.9 (d, 2C), 130.2 (s), 130.9 (d, 2C), 134.5 (s), 145.1
(s), 146.2 (s), 148.9 (s), 151.2 (s); MS (ESI+): m/z (%)=425
(100) (M+H)+, 155 (25); HRMS (EI+): m/z=425.1183,
calcd. for C22H20N2O5S: 425.1179.
Yield: 31% brown oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.59; IR (film): n=2934, 2235, 1739, 1365, 1168, 1090,
1019, 984, 901, 863, 783, 709, 659 cmÀ1 1H NMR (CDCl3,
;
4-Methyl-N-[2-(5-methylfuran-2-yl)ethyl]-N-pyridin-
4-ylethynylbenzenesulfonamide (5l)
300 MHz): d=2.20 (s, 3H), 2.44 (s, 3H), 2.91 (t, J=7.6 Hz,
2H), 3.65 (t, J=7.7 Hz, 2H), 5.80–5.83 (m, 1H), 5.92 (d, J=
2.9 Hz, d), 7.04 (dd, J=4.9 Hz, 1H), 7.23–7.26 (m, 1H), 7.33
(d, J=8.2 Hz, 2H), 7.37 (dd, J=3.0 Hz, 1H), 7.80 (d, J=
8.2 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz): d=13.53 (q),
21.67 (q), 27.23 (t), 50.36 (t), 65.94 (s), 81.25 (s), 106.1 (d),
107.6 (d), 121.5 (s), 125.1 (d), 127.6 (d, 2C), 128.9 (s), 129.8
(d, 2C), 130.3 (d), 134.7 (d), 144.6 (s), 149.3 (s), 151.1 (s);
MS (ESI): m/z (%)=408 (100) (M+Na)+, 345 (26), 301
(38); HR-MS (APCI): m/z=385.0806, calcd. for
C20H19rNO3S2: 385.0806.
Yield: 34%, dark oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.11; IR (film): n=2922, 2229, 1592, 1365, 1166, 1088,
815, 779, 676 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.20 (s,
1
N-(3-Methoxyphenylethynyl)-4-methyl-N-[2-(5-
methylfuran-2-yl)ethyl]benzenesulfonamide (5j)
3H), 2.45 (s, 3H), 2.98 (t, J=7.6 Hz, 2H), 3.70 (t, J=7.6 Hz,
2H), 5.81–5.83 (m, 1H), 5.93 (d, J=3.1 Hz, 1H), 7.18 (dd,
J=6.1 Hz, 1.4 Hz, 2H), 7.35 (d, J=8.3 Hz, 2H), 7.81 (d, J=
8.3 Hz, 2H), 8.51 (dd, J=6.1 Hz, 1.5 Hz, 2H); 13C NMR
(CDCl3, 75.5 MHz): d=13.49 (q), 21.75 (q), 27.47 (t), 50.26
(t), 70.82 (s), 88.03 (s), 106.3 (d), 107.8 (d), 123.6 (d, 2C),
127.6 (d, 2C), 129.9 (d, 2C), 130.3 (s), 130.9 (d, 2C), 134.5
(s), 145.2 (s), 146.3 (s), 148.8 (s), 151.3 (s); MS (EI+): m/z
(%)=380 (15) (M+), 225 (35), 109 (50), 95 (100); HR-MS
(ESI+): m/z=380.1195, calcd. for C21H20N2O3S: 380.1195.
Yield: 40%, brown oil; Rf (petroleum ether:ethyl acetate,
4-Bromo-N-(4-chlorophenylethynyl)-N-[2-(5-
methylfuran-2-yl)ethyl]benzenesulfonamide (5m)
˜
4:1)=0.43; IR (film): n=2921, 2549, 2236, 1365, 1168, 873,
1
785 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.21 (s, 3H), 2.43
(s, 3H), 2.99 (t, J=7.5 Hz, 2H), 3.67 (t, J=7.6 Hz, 2H), 3.81
(s, 3H), 5.81–5.83 (m, 1H), 5.93 (d, J=3.2 Hz, 1H), 76.81–
6.95 (m, 3H), 7.19 (t, J=8.1 Hz, 1H), 7.35 (d, J=8.4 Hz,
2H), 7.82 (d, J=8.3 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz):
d=13.55 (q), 21.76 (q), 27.35 (t), 50.21 (t), 55.29 (q), 106.1
(d), 107.6 (d), 114.1 (d), 116.3 (d), 123.9 (d), 127.7 (d, 2C),
129.3 (d), 129.8 (d, 2C), 134.6 (s), 144.7 (s), 149.2 (s), 151.1
Yield: 25%, yellow solid; mp 64–668C; Rf (petroleum
˜
ether:ethyl acetate, 4:1)=0.60; IR (film): n=2920, 2236,
1
1573, 1370, 1170, 1088, 1011, 825, 743, 600 cmÀ1; H NMR
(CDCl3, 300 MHz): d=2.20 (s, 3H), 2.96 (t, J=7.5 Hz, 2H),
3.69 (t, J=7.5 Hz, 2H), 5.80–5.83 (m, 1H), 5.92 (d, J=
3.2 Hz, 1H), 7.28 (s, 4H), 7.66–7.77 (m, 4H); 13C NMR
(CDCl3, 75.5 MHz): d=13.50 (q), 27.24 (t), 50.40 (t), 70.42
2866
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Gold Catalysis: Anellated Heterocycles and Dependency of the Reaction Pathway
FULL PAPERS
(q), 27.27 (t), 50.41 (t), 62.17 (s), 87.5 (s), 104.5 (d), 107.3
(s), 107.6 (d), 111.1 (d), 113.1 (d), 121.1 (d), 123.2 (d), 125.6
(d), 127.7 (d, 2C), 129.7 (s), 130.0 (d, 2C), 134.5 (s), 135.3
(s), 145.0 (s), 148.8 (s), 157.1 (s); MS (APCI): m/z (%)=434
(M+1)+ (34), 279 (100), 222 (31); HR-MS (APCI): m/z=
434.1422, calcd. for C24H23NO4S: 434.1428.
(s), 82.14 (s), 106.2 (d), 107.9 (d), 120.9 (s), 128.6 (d, 2C),
129.0 (d, 2C), 132.5 (d, 2C), 132.7 (d, 2C), 134.1 (s), 136.5
(s), 148.9 (s), 151.3 (s); MS (ESI+): m/z (%)=479 (6) (M+
2), 258 (30), 139 (58), 109 (46), 95 (100); anal. calcd. for
C21H17BrClNO3S: C 52.68, H 3.58, N 2.93; found: C 52.50, H
3.66, N 2.93. A crystal structure analysis was obtained.[6]
4-Bromo-N-[2-(5-methylfuran-2-yl)ethyl]-N-(1-
methyl-1H-indol-2-ylethynyl)benzenesulfonamide
(5p)
4-Bromo-N-[2-(5-methylfuran-2-yl)ethyl]-N-
naphthalen-1-ylethynylbenzenesulfonamide (5n)
Yield: 30%, colourless solid; mp 122–1248C; Rf (petroleum
˜
ether:ethyl acetate, 4:1)=0.52; IR (film): n=2218, 1572,
Yield: 27%, yellow oil; Rf (petroleum ether:ethyl acetate,
1
1365, 1169, 966 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.20
˜
4:1)=0.60; IR (film): n=3058, 2920, 2231, 1572, 1366, 1168,
1
1067, 1010, 932, 743, 706 cmÀ1; H NMR (CDCl3, 300 MHz):
(s, 3H), 3.00 (t, J=7.1 Hz, 2H), 3.72 (s, 3H), 3.76 (t, J=
7.2 Hz, 2H), 5.81–5.84 (m, 1H), 5.94 (d, J=3.0 Hz, 1H),
6.73 (s, 1H), 7.08–7.14 (m, 1H), 7.27 (dd, J=4.9 Hz, 1.0 Hz,
2H), 7.57 (td, J=7.7 Hz, 0.8 Hz, 1H), 7.68 (d, J=8.8 Hz,
2H), 7.76 (d, J=8.7 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz):
d=13.50 (q), 27.24 (t), 30.45 (q), 50.45 (t), 63.46 (s), 86.68
(s), 106.2 (d), 107.9 (d), 108.7 (d), 109.5 (d), 120.1 (d), 121.0
(d), 123.2 (d), 126.9 (s), 129.1 (d, 2C), 132.5 (d, 2C), 136.5
(s), 137.3 (s), 148.9 (s), 151.3 (s); MS (APCI): m/z (%)=499
(100) (M+1)+, 278 (46); HR-MS (APCI): m/z=496.0480,
calcd. for C24H21BrN2O3S: 496.0456.
d=2.21 (s, 3H), 3.07 (t, J=7.3 Hz, 2H), 3.80 (t, J=7.3 Hz,
2H), 5.81–5.83 (m, 1H), 5.96 (d, J=3.2 Hz, 1H), 7.38–7.44
(m, 1H), 7.50–7.59 (m, 3H), 7.66 (d, J=8.6 Hz, 2H), 7.77–
7.86 (m, 4H) , 8.13–8.16 (m, 1H); 13C NMR (CDCl3,
75.46 MHz): d=13.50 (q), 27.29 (t), 50.46 (t), 106.2 (d),
107.9 (d), 120.1 (s), 125.1 (s), 126.0 (d), 126.4 (d), 126.8 (d),
128.3 (d), 128.5 (d), 128.9 (s), 129.1 (d, 2C), 130.0 (d), 132.5
(d, 2C), 133.1 (s), 133.2 (s), 136.5 (s), 149.0 (s), 151.0 (s);
MS (ESI+): m/z (%)=495 (18) (M+2)+, 274 (100), 155 (46),
109 (44), 95 (52); HR-MS (ESI): m/z=493.0347, calcd. for
C25H20BrNO3S: 493.0338.
4-Bromo-N-[2-(5-methylfuran-2-yl)ethyl]-N-
phenanthren-9-ylethynylbenzenesulfonamide (5q)
N-Benzofuran-2-ylethynyl-N-[2-(5-ethylfuran-2-
yl)ethyl]-4-methylbenzenesulfonamide (5o)
Yield: 31%, sticky brown oil; Rf (petroleum ether:ethyl ace-
˜
tate, 4:1)=0.42; IR (film): n=3061, 2921, 2230, 1572, 1365,
Yield: 20%, brown oil; Rf (petroleum ether:ethyl acetate,
1168, 1067, 906, 742, 724, 567 cmÀ1 1H NMR (CDCl3,
;
˜
4:1)=0.32; IR (film): n=2253, 1368, 1168, 1090, 902, 723,
300 MHz): d=2.22 (s, 3H), 7.40 (t, J=7.4 Hz, 2H), 3.83 (t,
J=7.4 Hz, 2H), 5.81–5.83 (m, 1H), 5.98 (d, J=3.1 Hz, 1H),
7.56–7.73 (m, 6H), 7.80–7.85 (m, 3H), 7.88 (s, 1H), 8.24–
8.28 (m, 1H), 8.62–8.71 (m, 2H); 13C NMR (CDCl3,
75.5 MHz): d=13.61 (q), 27.36 (t), 50.54 (t), 70.02 (s), 85.37
(s), 106.2 (d), 107.9 (d), 118.9 (s), 122.6 (d), 122.9 (d), 126.7
(d), 127.0 (d), 127.1 (d), 127.2 (d), 127.4 (d), 128.3 (d), 128.9
649 cmÀ1 1H NMR (CD2Cl2, 300 MHz): d=1.16 (t, J=
;
7.6 Hz, 3H), 2.46 (s, 3H), 2.55 (q, J=7.6 Hz, 2H), 2.96 (t,
J=7.4 Hz, 2H), 3.70 (t, J=7.4 Hz, 2H), 5.84–5.86 (m, 1H),
5.96 (d, J=3.1 Hz, 1H), 6.96 (d, J=1.1 Hz, 1H), 7.22–7.47
(m, 5H), 7.56 (d, J=7.7 Hz, 1H), 7.80 (d, J=8.3 Hz, 2H);
13C NMR (CDCl3, 75.5 MHz): d=12.09 (q), 21.33 (t), 21.78
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FULL PAPERS
was removed under vacuum. Column chromatography
(silica gel, petroleum ether:ethyl acetate) furnished the pure
product as a light brown oil; yield: 110 mg (48%); Rf (petro-
˜
leum ether:ethyl acetate, 2:1)=0.23; IR (film): n=3523,
2972, 2241, 1360, 1165, 998, 847, 813, 677, 573 cmÀ1
;
1H NMR (CD2Cl2, 250 MHz): d=1.18 (t, J=7.6 Hz, 3H),
2.43 (s, 3H), 2.56 (q, J=7.6 Hz, 2H), 2.88 (t, J=7.2 Hz,
2H), 3.57 (t, J=7.3 Hz, 2H), 4.33 (d, J=5.5 Hz, 2H), 5.83–
5.86 (m, 1H), 5.91 (d, J=3.1 Hz, 1H), 7.35 (d, J=8.6 Hz,
2H), 7.75 (d, J=8.5 Hz, 2H); 13C NMR (CDCl3, 62.9 MHz):
d=12.12 (q), 21.32 (t), 21.65 (q), 27.26 (t), 50.09 (t), 51.22
(t), 69.95 (s), 78.87 (s), 104.4 (d), 107.4 (d), 127.5 (d, 2C),
129.9 (d, 2C), 134.6 (s), 144.7 (s), 149.1 (s), 157.0 (s); MS
(APCI): m/z (%)=348 (6) (M+1)+, 330 (100); HR-MS
(ESI): m/z=330.1145 (water molecule lost), cacd. for
C18H21NO4S: 347.1191.
(s), 129.1 (d, 2C), 130.0 (s), 131.1 (s), 131.3 (d), 132.5 (d,
2C), 136.5 (s), 149.0 (s), 151.3 (s); MS (APCI): m/z (%)=
544 (8) (M+), 325 (100), 282 (42); HR-MS (APCI): m/z=
544.0573, C29H22BrNO3S: 544.0579.
N-(4-Methoxyphenylethynyl)-4-methyl-N-[3-(5-
methylfuran-2-yl)propyl]benzenesulfonamide (5t)
N-(2-Furan-2-ylethyl)-4-methyl-N-4-
tolylethynylbenzenesulfonamide (5r)
Yield: 41%, brown oil; Rf (petroleum ether:ethyl acetate,
˜
8:1)=0.34; IR (film): n=2922, 2235, 1597, 1363, 1167, 1090,
1
814, 735, 664 cmÀ1; H NMR (CD2Cl2, 300 MHz): d=2.34 (s,
Yield: 37%, brown oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.47; IR (film): n=2922, 2235, 1604, 1511, 1361, 1287,
3H), 2.44 (s, 3H), 3.01 (t, J=7.4 Hz, 2H), 3.66 (t, J=7.4 Hz,
2H), 6.08–6.10 (m, 1H), 6.27–6.30 (m, 1H), 7.12 (d, J=
8.4 Hz, 2H), 7.25 (d, J=8.2 Hz, 2H), 7.31 (dd, J=1.9,
0.7 Hz, 1H), 7.37 (d, J=8.4 Hz, 2H), 7.78 (d, J=8.4 Hz,
2H); 13C NMR (CDCl3, 75.5 MHz): d=21.47 (q), 21.73 (q),
27.15 (t), 50.06 (t), 71.01 (s), 81.13 (s), 106.9 (d), 109.3 (d),
127.7 (d, 2C), 129.0 (d, 2C), 129.8 (d, 2C), 131.5 (d, 2C),
134.5 (s), 138.1 (s), 141.6 (d), 144.6 (d), 151.3 (d); MS
(ESI+): m/z (%)=375 (7), 360 (6), 304 (100); HR-MS
(APCI): m/z=402.1635, calcd. for C22H21NO3S: 402.1639.
1246, 1166, 1090, 1020, 831, 722, 663, 577 cmÀ1 1H NMR
;
(CD2Cl2, 250 MHz): d=2.01 (qu, J=7.2 Hz, 2H), 2.23 (s,
3H), 2.45 (s, 3H), 2.65 (t, J=7.3 Hz, 2H), 3.42 (t, J=7.1 Hz,
2H), 3.80 (s, 3H), 5.81–5.85 (m, 1H), 5.88 (d, J=3.0 Hz,
1H), 6.82 (d, J=8.8 Hz, 2H), 7.28–7.38 (m, 4H), 7.82 (d, J=
8.6 Hz, 2H); 13C NMR (CDCl3, 62.9 MHz): d=13.56 (q),
21.74 (q), 24.92 (t), 26.61 (t), 51.07 (t), 55.35 (q), 70.41 (s),
80.92 (s), 105.8 (d), 106.1 (d), 113.9 (d, 2C), 114.7 (s), 127.7
(d, 2C), 129.7 (d, 2C), 133.4 (d, 2C), 134.5 (s), 144.5 (s),
150.5 (s), 152.6 (s), 159.5 (s); MS (APCI): m/z (%)=424
(100) (M+1)+; HR-MS (ESI): m/z=423.1499, calcd. for
C24H25NO4S: 423.1504.
N-[2-(5-Ethylfuran-2-yl)ethyl]-N-(3-hydroxyprop-1-
ynyl)-4-methylbenzenesulfonamide (5s)
4-Methyl-N-[3-(5-methylfuran-2-yl)propyl]-N-p-
tolylethynylbenzenesulfonamide (5u)
210 mg (0.66 mmol, 1 equiv.) of the alkyne 1c were dissolved
in 10 mL dry THF taken in a flame-dried-round bottom
flask under nitrogen. The solution was cooled to À788C and
0.29 mL (0.73 mmol, 1.1 equiv.) n-butyllithium (2.5M solu-
tion in hexane) were added dropwise. The solution was
stirred for 45 min at the same temperature and then 40 mg
(1.2 mmol, 2 equiv.) of paraformaldehyde were added in
portions. The reaction mixture was warmed to room temper-
ature and stirred for overnight. After being quenched with
ammonium chloride solution the mixture was extracted with
ether. After being dried over magnesium sulfate the solvent
Yield: 24%, yellow oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.55; IR (film): n=2924, 2235, 1448, 1363, 1166, 1090,
1
907, 814, 727, 662, 576 cmÀ1; H NMR (CD2Cl2, 250 MHz):
d=1.99 (qu, J=7.3 Hz, 2H), 2.21 (s, 3H), 2.33 (s, 3H), 2.44
(s, 3H), 2.63 (t, J=7.3 Hz, 2H), 3.41 (t, J=7.3 Hz, 2H),
2868
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Gold Catalysis: Anellated Heterocycles and Dependency of the Reaction Pathway
FULL PAPERS
5.82–5.85 (m, 1H), 5.87 (d, J=3.1 Hz, 1H), 7.11 (d, J=
8.4 Hz, 2H), 7.25 (d, J=8.3 Hz, 2H), 7.37 (d, J=8.4 Hz,
2H), 7.80 (d, J=8.3 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz):
d=13.47 (q), 21.43 (q), 21.67 (q), 24.87 (t), 26.60 (t), 50.99
(t), 70.72 (s), 81.61 (s), 105.8 (d), 106.1 (d), 119.7 (s), 127.7
(d, 2C), 129.0 (d, 2C), 129.7 (d, 2C), 131.5 (d, 2C), 134.5
(s), 138.0 (s), 144.5 (s), 150.5 (s), 152.6 (s); MS (ESI): m/z
(%)=430 (M+Na)+ 408 (18); HR-MS (ESI): m/z=
407.1550, calcd. for C24H25NO3S: 407.1555.
HR-MS (ESI): m/z=394.1349, calcd. for C22H22N2O3S:
394.1351.
4-Methyl-N-[3-(5-methylfuran-2-yl)propyl]-N-
naphthalen-1-ylethynylbenzenesulfonamide (5x)
Yield: 35%, brown oil; Rf (petroleum ether:ethyl acetate,
4-Methyl-N-[3-(5-methylfuran-2-yl)propyl]-N-
thiophen-3-ylethynylbenzenesulfonamide (5v)
˜
4:1)=0.54; IR (film): n=3058, 2922, 2230, 1596, 1569, 1448,
1
1363, 1167, 1090, 1018, 951, 774, 669 cmÀ1; H NMR (CDCl3,
300 MHz): d=2.03–2.15 (m, 2H), 2.22 (s, 3H), 2.44 (s, 3H),
2.70 (t, J=7.6 Hz, 2H), 3.54 (t, J=7.2 Hz, 2H), 5.83–5.87
(m, 1H), 5.91 (d, J=3.1 Hz, 1H), 7.38 (d, J=7.8 Hz, 2H),
7.43 (d, J=7.8 Hz, 1H), 7.50–7.59 (m, 3H), 7.81 (d, J=
8.6 Hz, 2H), 7.87 (d, J=8.3 Hz, 2H), 8.15–8.20 (m, 1H);
13C NMR (CDCl3, 75.5 MHz): d=13.62 (q), 21.74 (q), 24.92
(t), 26.70 (t), 50.99 (t), 69.26 (s), 86.82 (s), 105.8 (d), 106.2
(d), 120.5 (s), 125.2 (d), 126.2 (d), 126.3 (d), 126.7 (d), 127.0
(s), 127.7 (d, 2C), 128.1 (d), 128.2 (d), 129.6 (d), 129.8 (d,
2C), 133.1 (s), 134.5 (s), 144.7 (s), 150.6 (s), 152.5 (s); MS
(ESI): m/z (%)=466 (26) (M+Na)+, 444 (100) (M+1)+;
HR-MS (ESI): m/z=443.1550, calcd. for C27H25NO3S:
443.1555.
Yield: 39%, yellow oil; Rf (petroleum ether:ethyl acetate,
˜
4:1)=0.55; IR (film): n=3106, 2921, 2236, 1597, 1569, 1363,
1
1167, 1091, 781 658, 579 cmÀ1; H NMR (CDCl3, 300 MHz):
d=1.97 (quint, J=7.2 Hz, 2H), 2.21 (s, 3H), 2.45 (s, 3H),
2.62 (t, J=7.4 Hz, 2H), 3.41 (t, J=7.2 Hz, 2H), 5.82–5.85
(m, 1H), 5.87 (d, J=3.0 Hz, 1H), 7.06 (dd, J=5.1 Hz,
1.1 Hz, 1H), 7.27–7.31 (m, 1H), 7.35–7.41 (m,3H), 7.79 (d,
J=8.8 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz): d=13.49 (q),
21.65 (q), 24.83 (t), 26.57 (t), 50.98 (t), 65.74 (s), 81.59 (s),
105.8 (d), 106.1 (d), 121.5 (s), 125.1 (d), 127.7 (d, 2C), 128.7
(d), 129.7 (d, 2C), 130.2 (d), 134.5 (s), 144.5 (s), 150.5 (s),
152.5 (s); MS (ESI): m/z (%)=422 (100) (M+Na)+, 400
(23); HR-MS (ESI): m/z=399.0958, calcd. for C21H21NO3S2:
399.0963.
4-Methyl-N-[3-(5-methylfuran-2-yl)propyl]-N-prop-1-
ynylbenzenesulfonamide (5y)
4-Methyl-N-[3-(5-methylfuran-2-yl)propyl]-N-pyridin-
4-ylethynylbenzenesulfonamide (5w)
300 mg (0.95 mmol, 1 equiv.) of the ynamide were dissolved
in 10 mL of dry THF under nitrogen. The system was
cooled to À788C and 0.44 mL (1.1 mmol, 1.1 equiv.) of n-bu-
tyllithium were added slowly. The reaction mixture was
stirred for 45 min at the same temperature and then
0.31 mL (5 mmol, 5 equiv.) of methyl iodide were added.
The reaction mixture was warmed to room temperature in
12 h, and then quenched with saturated aqueous ammonium
chloride. The organic layer was extracted with ether, and
the extract dried over magnesium sulfate. The solvent was
removed under vacuum leaving the product as a yellow oil
which was directly used without further purification; yield:
307 mg (98%); Rf (petroleum ether:ethyl acetate, 8:1)=
Yield: 46%, dark brown oil; Rf (petroleum ether:ethyl ace-
˜
tate, 4:1)=0.10; IR (film): n=2922, 2229, 1592, 1366, 1167,
1
1089, 815, 675, 579, 545 cmÀ1; H NMR (CDCl3, 300 MHz):
d=1.95–2.06 (m, 2H), 2.22 (s, 3H), 2.45 (s, 3H), 2.63 (t, J=
7.4 Hz, 2H), 3.47 (t, J=7.4 Hz, 2H), 5.83–5.86 (m, 1H), 5.88
(d, J=3.1 Hz, 1H), 7.17–7.20 (m, 2H), 7.39 (d, J=8.4 Hz,
2H), 7.80 (d, J=8.5 Hz, 2H), 8.47–8.50 (m, 2H); 13C NMR
(CDCl3, 75.5 MHz): d=13.57 (q), 21.75 (q), 24.80 (t), 26.71
(t), 50.81 (t), 69.80 (s), 87.80 (s), 106.0 (d), 106.4 (d), 124.3
(d, 2C), 127.6 (d, 2C), 130.0 (d, 2C), 131.7 (s), 134.4 (s),
145.3 (s), 149.6 (d, 2C), 150.8 (s), 152.5 (s); MS (ESI): m/z
(%)=417 (90) (M+Na)+, 395 (100) (M+1)+, 240 (62);
˜
0.54; IR (film): n=2253, 1968, 1360, 1169, 902, 723,
1
649 cmÀ1; H NMR (CDCl3, 300 MHz): d=1.89 (s, 3H), 1.93
(quint, J=7.4 Hz , 2H), 2.24 (s, 3H), 2.44 (s, 3H), 2.60 (t,
J=7.4 Hz, 2H), 3.29 (t, J=7.4 Hz, 2H), 5.81–5.84 (m, 1H),
5.87 (d, J=3.1 Hz, 1H), 7.33 (d, J=8.4 Hz, 2H), 7.76 (d, J=
8.4 Hz, 2H); 13C NMR (CDCl3, 75.46 MHz): d=3.31 (q),
13.51 (q), 21.62 (q), 24.82 (t), 26.42 (t), 50.81 (t), 65.78 (s),
Adv. Synth. Catal. 2009, 351, 2855 – 2875
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A. Stephen K. Hashmi et al.
FULL PAPERS
71.84 (s), 105.8 (d), 106.0 (d), 127.5 (d, 2C), 129.6 (d, 2C),
134.6 (s), 144.3 (s), 150.5 (s), 152.8 (s); MS (APCI): m/z
(%)=332 (100) (M+1) +, 177 (25); HR-MS (ESI): m/z=
331.1239, calcd. for C18H21NO3S: 331.1241.
(d), 111.3 (d), 118.0 (d), 125.6 (s), 127.3 (d, 2C), 129.3 (s),
129.7 (d, 2C), 130.1 (d), 130.6 (s), 132.7 (s), 133.9 (s), 137.9
(s), 144.2 (s), 157.5 (s), 205.5 (s); MS (ESI+): m/z (%)=432
(M+Na)+ (100), 276 (39), 254 (41); HR-MS (ESI+): m/z=
432.1240, calcd. for C23H23NO4S: 432.1245.
Catalysis; General Procedure
1-[10-(Toluene-4-sulfonyl)-9,10-dihydro-8H-10-
azacyclopenta[b]phenanthren-7-yl]propan-2-one (7c)
500 mmol (1 equiv.) of the substrate 5 was dissolved in
CH2Cl2 or CHCl3 and 25 mmol (5 mol%) of Ph3PAuCl were
added, followed by 25 mmol (5 mol%) of AgBF4. The reac-
tion mixture was stirred at room temperature or as men-
tioned until the starting material was consumed. The solvent
was removed under vacuum and the product was purified
over flash column chromatography (silica gel, petroleum
ether:ethyl acetate).
1-[6-Methyl-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
benzo[f]indol-4-yl]propan-2-one (7a)
White solid; mp 202–2058C; Rf (petroleum ether:ethyl ace-
˜
tate, 2:1)=0.11; IR (film): n=2923, 2253, 1711, 1454, 1352,
1
1162, 1090, 905, 670 cmÀ1; H NMR (CDCl3, 300 MHz): d=
2.04 (s, 3H), 2.31 (s, 3H), 3.04 (t, J=8.2 Hz, 2H), 3.99 (s,
2H), 4.07 (t, J=8.2 Hz, 2H), 7.18 (d, J=8.2 Hz, 2H), 7.58–
7.73 (m, 4H), 7.76 (d, J=8.3 Hz, 2H), 7.88 (dd, J=7.8 Hz,
1.3 Hz, 1H), 8.77 (d, J=8.4 Hz, 1H), 8.91 (s, 1H); 13C NMR
(CDCl3, 75.5 MHz): d=21.52 (q), 27.30 (t), 29.31 (q), 45.48
(t), 49.92 (t), 106.8 (d), 121.5 (d), 123.2 (d), 126.4 (d), 126.8
(d), 127.3 (d, 2C), 127.4 (s), 127.8 (s), 128.4 (d), 129.7 (d,
2C), 130.4 (s), 131.4 (s), 131.7 (s), 132.0 (s), 133.9 (s), 140.7
(s), 144.3 (s), 205.2 (s); MS (ESI+): m/z (%)=430 (M+1)+
(29), 429 (M+) (100), 217 (45); HR-MS (ESI+): m/z=
430.1479, calcd. for C26H23NO3S: 430.1469.
White solid; mp 158–1608C; Rf (petroleum ether:ethyl ace-
˜
tate, 2:1)=0.18; IR (film): n=2923, 1717, 1351, 1163, 1091,
914, 814, 664, 596 cmÀ1 1H NMR (CDCl3, 500 MHz): d=
;
2.02 (s, 3H), 2.33 (s, 3H), 2.48 (s, 3H), 2.98 (t, J=8.2 Hz,
2H), 3.91 (s, 2H), 4.00 (t, J=8.2 Hz, 2H), 7.19 (d, J=
8.3 Hz, 2H), 7.29 (d, J=8.3 Hz, 2H), 7.47 (s, 1H), 7.69–7.77
(m, 3H), 7.91 (s, 1H); 13C NMR (CDCl3, 125 MHz): d=
21.54 (q), 21.99 (q), 27.19 (t), 29.24 (q), 45.01 (t), 47.02 (t),
110.8 (d), 122.2 (d), 126.2 (s), 127.3 (d, 2C), 128.2 (d), 128.5
(d), 129.7 (d, 2C), 132.2 (s), 132.4 (s), 133.9 (s), 135.0 (s),
138.9 (s), 144.2 (s), 205.5 (s); MS (ESI+): m/z (%)=416
1-[2-Methyl-7-(toluene-4-sulfonyl)-6,7-dihydro-5H-1-
oxa-7-aza-s-indacen-4-yl]propan-2-one (7d)
(M+Na) CHTUNGTRENNUNG
+A(100), 394 (7); HRMS (ESI+): m/z=416.1298,
calcd. for C23H23NO3S: 416.1296.
1-[6-Methoxy-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
benzo[f]indol-4-yl]propan-2-one (7b)
Yellow oil; Rf (petroleum ether:ethyl acetate, 2:1)=0.11; IR
˜
(film): n=2923, 2253, 1978, 1711, 1355, 1163, 1093, 902, 723,
1
649 cmÀ1; H NMR (CDCl3, 300 MHz): d=1.99 (s, 3H), 2.35
(s, 3H), 2.43 (s, 3H), 2.79 (t, J=8.3 Hz, 2H), 3.63 (s, 2H),
3.98 (t, J=8.3 Hz, 2H), 6.24 (s,1H), 7.19 (d, J=8.2 Hz, 2H),
7.63–7.68 (m, 3H); 13C NMR (CDCl3, 75.5 MHz): d=14.23
(q), 21.50 (q), 26.40 (t), 29.14 (q), 46.11 (t), 5058 (t), 98.29
(d), 100.7 (d), 121.4 (s), 125.6 (s), 126.5 (s), 127.3 (d, 2C),
129.6 (d, 2C), 134.0 (s), 138.8 (s), 144.1 (s), 154.6 (s), 155.9
(s), 204.7 (s); MS (ESI+): m/z (%)=406 (89) (M+Na)+, 250
(85), 228 (100); HR-MS (ESI): m/z=406.1091, calcd. for
C21H21NO4S: 406.1088.
Yellow solid; mp 122–1248C; Rf (petroleum ether:ethyl ace-
˜
tate, 2:1)=0.17; IR (film): n=2922, 1706, 1613, 1413, 1347,
1
1233, 1160, 1088, 812, 662, 593, 543 cmÀ1; H NMR (CDCl3,
300 MHz): d=1.98 (s, 3H), 2.34 (s, 3H), 2.99 (t, J=8.1 Hz,
2H), 3.88 (s, 5H), 4.01 (t, J=8.1 Hz, 2H), 7.03 (d, J=
2.4 Hz, 1H), 7.14 (dd, J=8.9 Hz, 2.5 Hz, 1H), 7.20 (d, J=
8.2 Hz, 2H), 7.70 (d, J=8.3 Hz, 2H), 7.75 (d, J=8.9 Hz,
1H), 7.91 (s, 1H); 13C NMR (CDCl3, 75.5 MHz): d=21.51
(q), 27.40 (t), 29.08 (q), 45.56 (t), 49.67 (t), 55.39 (q), 102.6
1-[7-(Toluene-4-sulfonyl)-6,7-dihydro-5H-1-thia-7-aza-
s-indacen-4-yl]propan-2-one (7e)
Yellow oil; Rf (petroleum ether:ethyl acetate, 2:1)=0.19; IR
˜
(film): n=2924, 1710, 1597, 1430, 1353, 1253, 1161, 1091,
2870
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ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 2855 – 2875

Gold Catalysis: Anellated Heterocycles and Dependency of the Reaction Pathway
FULL PAPERS
(q), 46.33 (t), 50.43 (t), 107.4 (d), 120.8 (d), 125.2 (s), 126.2
(d), 128.5 (s), 128.6 (d, 2C), 129.4 (s), 132.4 (d, 2C), 135.9
(s), 136.0 (s), 139.2 (s), 140.5 (s), 204.5 (s); MS (ESI+): m/z
(%)=471 (100) (M+Na)+, 231 (78); HR-MS (ESI): m/z=
448.9752, calcd. for C19H16BrNO3S2: 448.9750.
1-[5-(4-Bromobenzenesulfonyl)-6,7-dihydro-5H-1-
thia-5-aza-s-indacen-8-yl]propan-2-one (7h)
1
1065, 905, 729, 662 cmÀ1; H NMR (CDCl3, 300 MHz): d=
2.03 (s, 3H), 2.35 (s, 3H), 2.89 (t, J=8.2 Hz, 2H), 3.82 (s,
2H), 4.01 (t, J=8.2 Hz, 2H), 7.19–7.24 (m, 3H), 7.38 (d, J=
5.6 Hz, 1H), 7.69 (d, J=8.3 Hz, 2H), 8.07 (s, 1H); 13C NMR
(CDCl3, 75.5 MHz): d=21.56 (q), 26.60 (t), 29.28 (q), 46.39
(t), 50.39 (t), 107.4 (d), 120.8 (d), 125.0 (s), 125.9 (d), 127.3
(d, 2C), 129.5 (s), 129.7 (d, 2C), 133.9 (s), 135.7 (s), 139.7
(s), 140.5 (s), 144.3 (s), 204.6 (s); MS (ESI+): m/z (%): 408
(M+Na)+ (27), 253 (50), 230 (71), 188 (100); HR-MS
(ESI+): m/z=386.0879, calcd. for C20H19NO3S2: 386.0886.
Yellow oil; Rf (petroleum ether:ethyl acetate, 2:1)=0.17; IR
˜
(film): n=3086, 1873, 1716, 1573, 1357, 1253, 1168, 1093,
1
1067, 909, 826, 738, 612 cmÀ1; H NMR (CDCl3, 300 MHz):
1-[1-(4-Bromobenzenesulfonyl)-6-methoxy-2,3-
dihydro-1H-benzo[f]indol-4-yl]propan-2-one (7f)
d=2.12 (s,3H), 2.89 (t, J=8.2 Hz; 2H), 3.79 (s, 2H), 4.00 (t,
J=8.2 Hz, 2H), 7.34 (d, J=5.5 Hz, 1H), 7.43 (d, J=5.5 Hz,
1H), 7.56 (d, J=8.6 Hz, 2H), 7.66 (d, J=8.7 Hz, 2H), 7.98
(s, 1H); 13C NMR (CDCl3, 75.5 MHz): d=26.58 (t), 29.67
(q), 47.41 (t), 50.41 (t), 108.5 (d), 124.8 (s), 125.0 (d), 126.4
(d), 128.4 (s), 128.6 (d, 2C), 129.5 (s), 132.4 (d, 2C), 135.9
(s), 136.6 (s), 139.8 (s), 139.9 (s), 203.9 (s); MS (APCI): m/z
(%)=452 (27) (M+1)+, 246 (22), 231 (100); HR-MS
(APCI): m/z=449.9829, calcd. for C19H16BrNO3S2: 449.9834.
1-[5-(Toluene-4-sulfonyl)-6,7-dihydro-5H-1-thia-5-aza-
s-indacen-8-yl]propan-2-one (7i)
Pale yellow solid; mp 110–1148C; Rf (petroleum ether:ethyl
˜
acetate, 2:1)=0.14; IR (film): n=2935, 1707, 1614, 1573,
1355, 1235, 1168, 1091, 738 cmÀ1 1H NMR (CDCl3,
;
300 MHz): d=2.01 (s, 3H), 2.99 (t, J=8.1 Hz, 2H), 3.89 (s,
5H), 4.01 (t, J=8.1 Hz, 2H), 7.03–7.05 (m, 1H), 7.15 (dd,
J=8.6 Hz, 2.4 Hz, 1H), 7.55 (d, J=8.6 Hz, 2H), 7.68 (d, J=
8.6 Hz, 2H), 7.75 (d, J=8.7 Hz, 1H), 7.89 (s, 1H); 13C NMR
(CDCl3, 75.5 MHz): d=27.36 (t), 29.18 (q), 45.53 (t), 49.86
(t), 55.47 (q), 102.6 (d), 111.3 (d), 118.2 (d), 125.9 (s), 128.4
(s), 128.7 (d, 2C), 129.3 (s), 130.1 (d), 130.8 (s), 132.4 (d,
2C), 135.9 (s), 137.5 (s), 157.9 (s), 205.1 (s); MS (ESI): m/z
(%)=473 (5) (M+), 255 (100); HR-MS (ESI): m/z=
496.0189, calcd. for C22H20BrNO4S: 496.0189.
Yellow oil; Rf (petroleum ether:ethyl acetate, 2:1)=0.18; IR
(film): n˜ =2958, 2924, 1713, 1597, 1402, 1352, 1253, 1160,
1089, 909, 813, 729, 664, 588 cmÀ1
;
1H NMR (CDCl3,
300 MHz): d=2.09 (s, 3H), 2.35 (s, 3H), 2.86 (t, J=8.1 Hz,
2H), 3.77 (s, 2H), 4.00 (t, J=8.1 Hz, 2H), 7.20 (d, J=
8.3 Hz, 2H), 7.34 (d, J=5.4 Hz, 1H), 7.41 (d, J=5.4 Hz,
1H), 7.68 (d, J=8.3 Hz, 2H), 8.00 (s, 1H); 13C NMR
(CDCl3, 75.5 MHz): d=21.54 (q), 26.61 (t), 29.51 (q), 47.48
(t), 50.45 (t), 108.5 (d), 124.5 (s), 125.0 (d), 126.1 (d), 127.3
(d, 2C), 129.7 (d, 2C), 130.2 (s), 134.0 (s), 137.4 (s), 139.9
(s), 144.1 (s), 204.3 (s); MS (ESI): m/z (%)=408 (100) (M+
Na)+; HR-MS (APCI): m/z=385.0802, calcd, for
C20H19rNO3S2: 385.0806.
1-[7-(4-Bromobenzenesulfonyl)-6,7-dihydro-5H-1-
thia-7-aza-s-indacen-4-yl]propan-2-one (7g)
Yellow solid; mp 182–1858C; Rf (petroleum ether:ethyl ace-
1-[7-Methoxy-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-
benzo[f]indol-4-yl]propan-2-one (7j)
˜
tate, 2:1)=0.20; IR (film): n=2922, 2851, 1710, 1574, 1430,
1
1353, 1164, 1067 cmÀ1; H NMR (CDCl3, 300 MHz): d=2.06
(s, 3H), 2.92 (t, J=8.4 Hz, 2H), 3.84 (s, 2H), 4.01 (t, J=
8.4 Hz, 2H), 7.22 (d, J=5.5 Hz, 1H), 7.40 (d, J=5.6 Hz,
1H), 7.56 (d, J=8.6 Hz, 2H), 7.66 (d, J=8.6 Hz, 2H), 8.05
(s, 1H); 13C NMR (CDCl3, 75.5 MHz): d=26.54 (t), 29.33
Yellow solid; mp 116–1188C; Rf (petroleum ether:ethyl ace-
˜
tate, 2:1)=0.16; IR (film): n=2924, 1707, 1625, 1418, 1350,
1156, 1089, 813, 663, 596, 545 cmÀ1 1H NMR (CDCl3,
300 MHz): d=2.01 (s, 3H), 2.35 (s, 3H), 2.98 (t, J=8.2 Hz,
;
Adv. Synth. Catal. 2009, 351, 2855 – 2875
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2871

A. Stephen K. Hashmi et al.
FULL PAPERS
1332, 1162, 1090,904, 727 cmÀ1; H NMR (CDCl3, 300 MHz):
d=0.95 (t, J=7.2 Hz, 3H), 2.33–2.39 (m, 5H), 2.94 (t, J=
8.5 Hz, 2H), 4.00 (s, 2H), 4.05 (t, J=8.5 Hz, 2H), 7.22 (d,
J=8.4 Hz, 2H), 7.29 (dt, J=7.6 Hz, 1.1 Hz, 1H), 7.40 (dt,
J=7.8 Hz, 1.2 Hz, 1H), 7.56 (d, J=8.4 Hz, 1H), 7.72 (d, J=
8.3 Hz, 2H), 7.79 (d, J=8.1 Hz, 1H), 7.82 (s, 1H); 13C NMR
(CDCl3, 75.5 MHz): d=7.65 (q), 21.53 (q), 26.41 (t), 35.23
(t), 45.23 (t), 50.54 (t), 98.29 (d), 111.7 (d), 119.2 (s), 121.1
(d), 123.0 (d), 123.7 (s), 125.6 (s), 126.2 (d), 126.9 (s), 127.3
(d, 2C), 129.8 (d, 2C), 133.9 (s), 141.7 (s), 144.3 (s), 156.6
(s), 156.7 (s), 206.9 (s); MS (ESI+): m/z (%)=456 (100)
(M+Na)+, 300 (54), 278 (34), 222 (46), 179 (54); HR-MS
(ESI): m/z=456.1250. calcd. for C24H23NO4S: 456.1245.
1
2H), 3.90 (s, 2H), 3.93 (s, 3H), 4.00 (t, J=8.2 Hz, 2H), 7.06
(dd, J=8.9 Hz, 2.6 Hz, 1H), 7.17 (d, J=2.7 Hz, 1H), 7.22 (d,
J=8.2 Hz, 2H), 7.63 (d, J=8.9 Hz, 1H), 7.74 (d, J=8.3 Hz,
2H); 13C NMR (CDCl3, 75.5 MHz): d=21.53 (q), 26.86 (t),
29.24 (q), 45.19 (t), 49.83 (t), 55.34 (q), 107.1 (d), 109.8 (d),
117.6 (d), 124.5 (d), 124.6 (s), 126.#) (s), 127.3 (d, 2C), 129.7
(d, 2C), 134.0 (s), 135.8 (s), 140.4 (s), 144.3 (s), 157.8 (s),
205.3 (s); MS (ESI+): m/z (%)=410 (M+) (12), 255 (100);
HR-MS (ESI+): m/z=432.1243, calcd. for C23H23NO4S:
432.1245.
1-[1-(4-Bromobenzenesulfonyl)-9-methyl-1,2,3,9-
tetrahydropyrrolo
(7p)
ACHTUNGTRENN[UNG 2,3-b]carbazol-4-yl]propan-2-one
1-[10-(4-Bromobenzenesulfonyl)-9,10-dihydro-8H-10-
azacyclopenta[b]phenanthren-7-yl]propan-2-one (7n)
Pale yellow solid; mp 186–1888C; Rf (petroleum ether:ethyl
˜
acetate, 2:1)=0.23; IR (film): n=2925, 1722, 1599, 1570,
1469, 1440, 1354, 1318, 1160, 1065, 840, 816, 746 cmÀ1
;
1H NMR (CDCl3, 300 MHz): d=2.03 (s, 3H), 2.93 (t, J=
8.2 Hz, 2H), 3.88 (s, 3H), 4.05 (t, J=8.2 Hz, 2H), 4.10 (s,
2H), 7.18–7.24 (m, 1H), 7.39–7.48 (m, 2H), 7.53 (d, J=
8.6 Hz, 2H), 7.65 (d, J=8.7 Hz, 2H), 7.95 (d, J=7.9 Hz,
1H); 13C NMR (CDCl3, 75.5 MHz): d=26.44 (t), 29.14 (q),
29.49 (q), 46.58 (t), 50.65 (t), 95.25 (d), 108.6 (d), 119.5 (d),
121.3 (d), 121.9 (s), 123.7 (s), 125.1 (d), 125.7 (s), 126.3 (s),
128.6 (d, 2C), 132.4 (d, 2C), 136.1 (s), 140.1 (s), 141.5 (s),
141.8 (s), 160.2 (s), 205.2 (s); MS (APCI): m/z (%)=497
(90) (M+), 278 (100); HR-MS (APCI): m/z=496.0449, calcd.
for C24H21BrN2O3S: 496.0456.
Colourless solid; mp 186–1888C; Rf (petroleum ether:ethyl
˜
acetate, 2:1)=0.16; IR (film): n=2924, 1713, 1359, 1164,
1
1066, 821, 748, 615 cmÀ1; H NMR (CDCl3, 300 MHz): d=
2.07 (s, 3H), 3.06 (t, J=8.2 Hz, 2H), 4.01 (s, 2H), 4.06 (t,
J=8.2 Hz, 2H), 7.53 (d, J=8.6 Hz, 2H), 7.59–7.75 (m, 6H),
7.88 (dd, J=7.8 Hz, 1.1 Hz, 1H), 8.75 (d, J=8.3 Hz, 1H),
8.90 (s, 1H); 13C NMR (CDCl3, 75.5 MHz): d=27.25 (t),
29.44 (q), 45.37 (t), 49.93 (t), 106.9 (d), 121.5 (d), 123.1 (d),
126.6 (d), 126.9 (d), 127.0 (d), 127.6 (s), 128.0 (s), 128.5 (d),
128.6 (d, 2C), 130.3 (s), 131.3 (s), 131.7 (s), 131.8 (s), 132.4
(d, 2C), 135.8 (s), 140.1 (s), 205.1 (s); MS (APCI): m/z
(%)=494 (11) (M+), 275 (100); HR-MS (ESI): m/z=
493.0352, calcd, for C25H20BrNO3S: 493.0347.
1-[10-(4-Bromobenzenesulfonyl)-11,12-dihydro-10H-
10-azacyclopenta[b]triphenylen-13-yl]propan-2-one
(7q)
1-[1-(Toluene-4-sulfonyl)-2,3-dihydro-1H-9-oxa-1-
azacyclopenta[b]fluoren-4-yl]butan-2-one (7o)
Yellow solid; mp 134–1378C; Rf (petroleum ether:ethyl ace-
˜
tate, 2:1)=0.25, IR (film): n=2924, 1712, 1598, 1449, 1353,
Pale yellow solid; mp 108–1108C; Rf (petroleum ether:ethyl
˜
acetate, 2:1)=0.13; IR (film): n=3056, 2923, 1716, 1573,
1356, 1263, 1164, 733, 702, 568 cmÀ1 1H NMR (CDCl3,
;
300 MHz): d=2.29 (s, 3H), 2.93 (t, J=8.3 Hz, 2H), 4.02 (t,
J=8.3 Hz, 2H), 4.23 (s, 2H), 7.41–7.49 (m, 1H), 7.52–7.59
(m, 8H), 8.54–8.66 (m, 3H), 8.81 (s, 1H); 13C NMR (CDCl3,
75.5 MHz): d=27.46 (t), 29.80 (q), 49.86 (t), 106.7 (d), 123.0
2872
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Adv. Synth. Catal. 2009, 351, 2855 – 2875

Gold Catalysis: Anellated Heterocycles and Dependency of the Reaction Pathway
FULL PAPERS
(d), 123.7 (d), 125.7 (d), 126.3 (s), 126.7 (d), 126.9 (d), 127.5
(d), 127.6 (d), 128.6 (s), 128.7 (d, 2C), 129.1 (s), 129.9 (s),
130.0 (s), 130.6 (s), 132.1 (s), 132.5 (d, 2C), 133.5 (s), 135.7
(s), 140.6 (s), 165.2 (s), 205.6 (s); MS (APCI): m/z (%)=545
(62) (M+1)+, 306 (100), 280 (54); HR-MS (APCI): m/z=
544.0573, calcd. for C29H22BrNO3S: 544.0579.
4-Bromo-N-[2-(4-chlorophenyl)acetyl]-N-[2-(5-
methylfuran-2-yl)ethyl]benzenesulfonamide (8)
500 MHz): d=1.21–1.31 (m, 1H), 1.66–1.72 (m, 1H), 2.20 (s,
3H), 2.24–2.37 (m, 2H), 2.38 (s, 3H), 2.96–3–02 (m, 1H),
3.77 (s, 3H), 3.87 (td, J=13.6 Hz, 1H), 5.27 (s, 1H), 6.76 (d,
J=8.7 Hz, 2H), 7.05 (d, J=8.6 Hz, 2H), 7.11 (d, J=1.3 Hz,
1H), 7.17 (d, J=8.4 Hz, 2H), 7.34 (d, J=8.4 Hz, 2H);
13C NMR (CDCl3, 125 MHz): d=20.33 (t), 21.59 (q), 22.01
(q), 26.46 (q), 46.87 (t), 55.18 (q), 56.86 (d), 113.8 (d, 2C),
126.5 (s), 127.3 (d, 2C), 128.8 (s), 129.3 (d, 2C), 129.6 (d,
2C), 135.7 (s), 142.1 (d), 143.8 (s), 146.3 (s), 150.3 (s), 158.4
(s), 192.8 (s); MS (ESI): m/z (%)=424 (23) (M+1)+, 268
(100); HR-MS (ESI): m/z=446.1407, calcd. for C24H25NO4S:
446.1401.
Yellow oil; Rf (petroleum ether:ethyl acetate, 2:1)=0.38; IR
À1
˜
(film): n=2365, 2253, 1974, 1698, 1360, 1089, 902 cm
;
1H NMR (CDCl3, 300 MHz): d=2.21 (s, 3H), 3.00 (t, J=
7.1 Hz, 2H), 3.63 (s, 2H), 4.01 (t, J=7.1 Hz, 2H), 5.86–5.89
(m, 1H), 5.94 (d, J=3.0 Hz, 1H), 6.96 (d, J=8.5 Hz, 2H),
7.24 (d, J=8.5 Hz, 2H), 7.64 (d, J=8.6 Hz, 2H), 7.75 (d, J=
8.6 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz): d=13.51 (q),
28.76 (t), 41.70 (t), 46.21 (t), 106.4 (d), 108.3 (d), 128.8 (d,
2C), 129.1 (s), 129.6 (d, 2C), 130.7 (d, 2C), 131.3 (s), 132.3
(d, 2C), 133.3 (s), 138.2 (s), 149.2 (s), 151.5 (s), 170.5 (s);
MS (APCI): m/z (%)=498 (9) (M+2)+, 479 (20), 109 (100);
HR-MS (APCI): m/z=494.9900, calcd. for C21H19BrClNO4S:
494.9907.
1-[1-(Toluene-4-sulfonyl)-7-(4-tolyl)-2,3,4,7-
tetrahydro-1H-[1]pyrindin-6-yl]ethanone (10u)
N-Acryloyl-N-[2-(5-ethylfuran-2-yl)ethyl]-4-
methylbenzenesulfonamide (9)
Colourless solid; mp 165–1688C; Rf (petroleum ether:ethyl
˜
acetate, 2:1)=0.13; IR (film): n=2922, 2549, 2190, 1974,
1643, 1521, 1167, 809, 672, 552 cmÀ1 1H NMR (CDCl3,
;
500 MHz): d=1.22–1.31 (m, 1H), 1.66–1.73 (m, 1H), 2.19 (s,
3H), 2.30 (s, 3H), 2.38 (s, 3H), 2.31–2.37 (m, 2H), 2.95–3.02
(m, 1H), 3.86 (td, J=13.4 Hz, 3.7 Hz, 1H), 5.29 (s, 1H), 7.11
(d, J=1.5 Hz, 1H), 7.16 (d, J=8.3 Hz, 2H), 7.33 (d, J=
8.3 Hz, 2H); 13C NMR (CDCl3, 125 MHz): d=20.34 (t),
21.16 (q), 21.55 (q), 21.92 (t), 26.46 (q), 46.99 (t), 126.7 (s),
127.4 (d, 2C), 128.2 (d, 2C), 129.1 (d, 2C), 129.6 (d, 2C),
133.8 (s), 135.7 (s), 136.1 (s), 142.2 (d), 143.8 (s), 146.2 (s),
150.3 (s), 192.3 (s); MS (ESI): m/z (%)=430 (M+Na)+, 275
(28); HR-MS (ESI): m/z=407.1550, calcd. for C24H25NO3S:
407.1555.
Colourless oil; Rf (petroleum ether:ethyl acetate, 2:1)=
˜
0.35; IR (film): n=2970, 2934, 1684, 1346, 1159, 1087, 812,
1
709, 662 cmÀ1; H NMR (CDCl3, 300 MHz): d=1.19 (t, J=
7.8 Hz, 3H), 2.43 (s, 3H), 2.58 (q, J=7.8 Hz, 2H), 2.97–3.05
(m, 2H), 4.02–4.07 (m, 2H), 5.72 (dd, J=10.4 Hz, 1.8 Hz,
1H), 5.83–5.86 (m, 1H), 5.96 (d, J=3.1 Hz, 1H), 6.37 (dd,
J=16.7 Hz, 1.8 Hz, 1H), 6.72–6.82 (m, 1H), 7.32 (d, J=
8.4 Hz, 2H), 7.79 (d, J=8.4 Hz, 2H); 13C NMR (CDCl3,
75.5 MHz): d=12.40 (q), 21.70 (q), 29.17 (t), 46.00 (t), 104.9
(d), 107.7 (d), 128.0 (d, 2C), 128.7 (d), 130.1 (d, 2C), 131.1
(t), 137.1 (s), 145.6 (s), 150.0 (s), 157.5 (s), 165.6 (s); MS
(APCI): m/z (%)=348 (15) (M+1)+, 177 (22), 123 (100);
HR-MS (APCI): m/z=347.1172, calcd. for C18H21NO4S:
347.1191.
1-[7-Thiophen-3-yl-1-(toluene-4-sulfonyl)-2,3,4,7-
tetrahydro-1H-[1]pyrindin-6-yl]ethanone (10v)
Yellow solid; mp 180–1838C; Rf (petroleum ether:ethyl ace-
˜
tate, 2:1)=0.08; IR (film): n=2926, 1647, 1520, 1361, 1169,
1-[7-(4-Methoxyphenyl)-1-(toluene-4-sulfonyl)-2,3,4,7-
tetrahydro-1H-[1]pyrindin-6-yl]ethanone (10t)
1088, 1049, 831, 784, 731, 671 cmÀ1 1H NMR (CDCl3,
;
500 MHz): d=1.22–1.30 (m, 1H), 1.66–1.72 (m, 1H), 2.23 (s,
3H), 2.25–2.36 (m, 2H), 2.40 (s, 3H), 2.97–3.03 (m, 1H),
3.88 (td, J=13.6 Hz, 3.6 Hz, 1H), 5.50 (s, 1H), 6.77 (dd, J=
5.0 Hz, 1.3 Hz, 1H), 7.12 (d, J=1.3 Hz, 1H), 7.13–7.15 (m,
Yellow solid; mp 188–1938C; Rf (petroleum ether:ethyl ace-
˜
tate, 2:1)=0.23; IR (film): n=2932, 1646, 1509, 1362, 1299,
1247, 1168, 907, 820, 729, 672 cmÀ1
;
1H NMR (CDCl3,
Adv. Synth. Catal. 2009, 351, 2855 – 2875
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2873

A. Stephen K. Hashmi et al.
FULL PAPERS
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[4] For one other reaction with a phenyl group on the
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A. M. Echavarren, J. Am. Chem. Soc. 2003, 125, 5757–
5766.
1H), 7.17–7.18 (m, 1H), 7.21 (d, J=8.5 Hz, 2H), 7.38 (d, J=
8.5 Hz, 2H); 13C NMR (CDCl3, 75.5 MHz): d=20.29 (t),
21.55 (q), 21.90 (t), 26.41 (q), 46.85 (t), 52.87 (d), 122.9 (d),
124.7 (d), 126.4 (s), 126.7 (d), 127.3 (d, 2C), 129.7 (d, 2C),
135.6 (s), 136.5 (s), 142.2 (d), 143.9 (s), 144.9 (s), 149.3 (s),
192.3 (s); MS (ESI): m/z (%)=422 (100) (M+Na+)+, 400
(35) (M+1)+, 245 (12); HR-MS (ESI): m/z=399.0958,
calcd. for C21H21NO3S2: 399.0963.
4-Methyl-N-[3-(5-methylfuran-2-yl)propyl]-N-
propionylbenzenesulfonamide (11)
[5] For the few gold-catalyzed reactions with sulfur-con-
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[6] CCDC 734056 (5m), 734057 (7g) and 734058 (10u) con-
tain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Colourless oil; Rf (petroleum ether:ethyl acetate, 8:1)=
À1
˜
0.62; IR (film): n=2923, 1700, 1350, 1159, 903, 724 cm
;
1H NMR (CDCl3, 300 MHz): d=1.04 (t, J=7.2 Hz, 3H),
1.99–2.12 (m, 2H), 2.25 (s, 3H), 2.44 (s, 3H), 2.56 (q, J=
7.3 Hz, 2H), 2.64 (t, J=7.4 Hz, 2H), 3.83 (t, J=7.8 Hz, 2H),
7.32 (d, J=8.2 Hz, 2H), 7.76 (d, J=8.3 Hz, 2H); 13C NMR
(CDCl3, 125 MHz): d=8.840 (q), 13.52 (q), 21.59 (q), 23.45
(t), 28.27 (t), 29.68 (t), 59.04 (t), 105.3 (d), 105.9 (d), 127.5
(d, 2C), 129.8 (d, 2C), 133.7 (s); 143.2 (s), 151.7 (s), 157.8
(s), 180.0 (s); MS (ESI): m/z (%)=350 (24) (M+1)+, 332
(92), 294 (100); HR-MS (APCI): m/z=349.1334, calcd. for
C18H23NO4S: 349.1438.
[7] C. N. Oberhuber, P. P. Galn, E. H. Gmez, T. Lauter-
bach, C. Rodrguez, S. Lopez, C. Bour, A. Roselin, D. J.
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[9] Recently, a strong argument in favour of the cationic
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Acknowledgements
Gold salts were generously donated by Umicore AG & Co.
KG. T. Bender is grateful for support by the RISE program.
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