Synthesis of benzoindolines via a copper-catalyzed reaction of 1-bromoethynyl-2-(cyclopropylidenemethyl)arenes with N-allylsulfonamide

Article abstract of DOI:10.1002/adsc.201200374

A copper-catalyzed tandem reaction of 1-bromoethynyl-2- (cyclopropylidenemethyl)arenes with N-allylsulfonamide proceeds smoothly, affording functionalized benzoindolines in moderate to good yields. The transformation is a four-step cascade involving Ullma

Full text of DOI:10.1002/adsc.201200374

FULL PAPERS
DOI: 10.1002/adsc.201200374
Synthesis of Benzoindolines via a Copper-Catalyzed Reaction
of 1-Bromoethynyl-2-(cyclopropylidenemethyl)arenes with
N-Allylsulfonamide
Shaoyu Li,a Zhiming Li,a and Jie Wua,b,*
a
Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, Peopleꢀs Republic of China
Fax : (+86)-216-564-1740; e-mail: jie_wu@fudan.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
b
Sciences, 354 Fenglin Road, Shanghai 200032, Peopleꢀs Republic of China
Received: April 28, 2012; Revised: August 15, 2012; Published online: November 6, 2012
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200374.
Abstract: A copper-catalyzed tandem reaction of rangement, 6p-electrocyclization, and intramolecular
1-bromoethynyl-2-(cyclopropylidenemethyl)arenes
rearrangement.
with N-allylsulfonamide proceeds smoothly, afford-
ing functionalized benzoindolines in moderate to Keywords: N-allylsulfonamide; benzoindolines; 1-
good yields. The transformation is a four-step cas- bromoethynyl-2-(cyclopropylidenemethyl)arenes;
cade involving Ullmann coupling, aza-Claisen rear- copper(II) acetate; tandem reaction
Introduction
made to develop methods for the construction of the
benzoindoline framework.[3] Among the procedures
As an important class of heterocyclic compounds, the utilized, efficient pathways for the generation of func-
benzoindoline skeleton is found in many natural prod- tionalized benzoindolines with complexity and diver-
ucts and designed compounds with remarkable bio- sity are in great demand.
logical activities.[1,2] For instance, a structurally distinct
The tandem reaction, in which one transformation
class of indoline derivatives has been shown to pos- occurs sequentially after the other in the same reac-
sess 5HT2C/2B receptor antagonist activity, and as such tion vessel, has been widely pursued in the construc-
is believed to be of potential use in the treatment of tion of important heterocyclic skeletons.[4] It is well
CNS disorders, GI disorders and microvascular disor- recognized that the strained alkylidenecyclopropanes
ders.[2a,b] Recently, the National Institutes of Health are useful building blocks for the synthesis of a variety
investigated benzoindoline compounds as Shp2 inhibi- of carbocycles and heterocycles within complex mole-
tors for cancer therapy.[2d] Inspired by their diverse cules.[5–7] Similarly, 1-haloalkynes are versatile and
biological activities, continuous efforts have been useful synthons that have been widely applied in syn-
Scheme 1. A proposed synthetic route for the generation of fused benzoindoline derivatives.
Adv. Synth. Catal. 2012, 354, 3087 – 3094
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Shaoyu Li et al.
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thetic organic chemistry.[8,9] Encouraged by the ad-
vancement of tandem processes and the reactivities of
alkylidenecyclopropanes and 1-haloalkynes, we con-
ceived that 1-bromoethynyl-2-(cyclopropylideneme-
thyl)arenes, which incorporate alkylidenecyclopro-
pane and 1-haloalkyne in one molecule, would be
a good choice for the development of a new tandem
methodology to access functionalized benzoindolines.
Our strategy is illustrated in Scheme 1. Beginning
with readily accessible starting materials, we envi-
sioned that the reactive ketenimine B could be ob-
tained as well via an aza-Claisen rearrangement[10] of
the ynamine[11] intermediate A (Scheme 1). Retrosyn-
thetically, the intermediate A could be generated via
a copper-catalyzed Ullmann reaction[12] of 1-bromo-
Table 1. Initial studies for the copper-catalyzed reaction of
1-bromoethynyl-2-(cyclopropylidenemethyl)-4-methylben-
zene 1a with N-allyl-4-methylbenzenesulfonamide 2a.
ACHTUNGTRENNUNGethynyl-2-(cyclopropylidenemethyl)arene 1 with allyl-
ic amine 2. If the ketenimine B could be formed as
expected, a consecutive 6p-electrocyclization[13] would
then occur to form intermediate C, which would sub-
sequently undergo an intramolecular rearrangement
to produce the fused benzoindoline 3. Although there
are several competing pathways in the proposed pro-
cess, the attractiveness of indoline 3 and the challenge
of the tandem synthetic route described in Scheme 1
prompted us to investigate the feasibility of this pro-
posed conversion.
Entry [Cu]
Ligand Base
Solvent Yield [%][a]
1[b]
2
3
4
5
6
7
8
9
CuSO4
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
K3PO4
K3PO4
K2CO3
Cs2CO3
Na2CO3
toluene trace
toluene 20
toluene 39
CuSO4
CuSO4
CuSO4
CuSO4
CuSO4
CuSO4
CuSO4
CuSO4
CuSO4
CuACTHNUTRGEN(UNG OAc)2 L1
CuI
CuBr
CuCl
CuCl2
CuBr2
toluene
7
toluene N.D.
NaO-t-Bu toluene trace
LiOH
toluene 21
toluene 22
toluene trace
toluene 38
toluene 54
toluene 30
toluene 43
toluene 38
toluene 39
toluene 22
toluene 38
toluene 36
toluene 32
toluene 15
toluene 25
toluene trace
toluene trace
dioxane 65
KHCO3
KOAc
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
10[c]
11
12
13
14
15
16
17
18[d]
19
20
21
22
23
24
25
26
Results and Discussion
L1
L1
L1
L1
L1
The initial experiment evaluated the reaction of 1-
(bromoethynyl)-2-(cyclopropylidenemethyl)-4-methyl-
benzene 1a with N-allyl-4-methylbenzenesulfonamide
2a catalyzed by copper sulfate (10 mol%) with 1,10-
phenanthroline (20 mol%) as ligand in the presence
of K3PO4 in toluene at 808C (Table 1, entry 1). Un-
fortunately, only a trace amount of the desired prod-
uct 3a was detected and most of the observed species
were the Ullman coupling products (intermediate A).
However, when the reaction temperature was in-
creased to 1108C, the expected indoline 3a was isolat-
ed as the major product, albeit in low yield (20%,
Table 1, entry 2). Encouraged by this promising result,
we tried to further optimize the reaction conditions.
Various bases were examined in this tandem process,
and the results indicated that K2CO3 was the best
choice (Table 1, entries 3–9). Only a trace amount of
product was observed when a strong base such as
NaO-t-Bu was used. The outcome could not be im-
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Cu
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
G
AHCTUNGTRENNUNG
DMF
73
DMSO 60
[a]
Isolated yield based on N-allyl-4-methylbenzenesulfon-
AHCTUNGTRENNaGUN mide 2a.
The reaction was performed at 808C.
The ratio of 1a/2a was 1.5.
In the presence of CuACHTNUGTRENUNG(OAc)2 (5 mol%).
[b]
[c]
[d]
proved when the ratio of substrates was increased to entry 18). In contrast to 1,10-phenanthroline, other
1.5:1 (Table 1, entry 10). The yield was increased to Ullmann coupling ligands gave rise to inferior results
54% when copper sulfate was replaced by copper ace- (Table 1, entries 19–23). Solvent screening revealed
tate as catalyst (Table 1, entry 11). However, inferior that polar solvents favor the reaction process. In par-
results were obtained when other copper(I) or cop- ticular, use of DMF improved the yield to 73%
per(II) salts were employed (Table 1, entries 12–17). (Table 1, entries 24–26).
The yield decreased dramatically when the amount of
With the optimized reaction conditions in hand (as
copper acetate was reduced to 5 mol% (Table 1, highlighted in Table 1, entry 25), we set out to explore
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Adv. Synth. Catal. 2012, 354, 3087 – 3094

Synthesis of Benzoindolines via a Copper-Catalyzed Reaction
Table 2. Copper-catalyzed reaction of 1-2-bromoethynyl-2-
(cyclopropylidenemethyl)arene 1 with N-allylsulfonamide 2.
Entry Substrate 1
R2, R3
Yield
[%][a]
Figure 1. Structure of TS.
1
2
3
4
5
H, Ts (2a)
H, Ts (2a)
H, Ts (2a)
H, Ts (2a)
H, Ts (2a)
73 (3a)
66 (3b)
65 (3c)
70 (3d)
66 (3e)
tory results (Table 2, entries 3–5). However, the reac-
tion of thiophenyl-incorporated substrate 1f with N-
allyl-4-methylbenzenesulfonamide 2a provided the
corresponding product in relatively low 30% yield
(Table 2, entry 6). With respect to the scope of the R2
group in substrate 2, but-2-en-1-amide 2b reacted ef-
fectively with substrate 1a, generating the expected
product 3g in 60% yield (Table 2, entry 7). A better
yield was observed when 3-phenylprop-2-en-1-amide
2c was employed as a replacement (3h, 75%; Table 2,
entry 8). With respect to the R3 group in substrate 2,
the reaction of N-allyl amide 2d or 2e with 1-(bro-
moethynyl)-2-(cyclopropylidenemethyl)-4-methylben-
zene 1a afforded the corresponding products 3i and 3j
in good yields, respectively (Table 2, entries 9 and 10).
In contrast, only a trace amount of desired product
was detected when amide 2f was used in the reaction
(R3 =4-nitrobenzenesulfonyl group, Table 2, entry 11).
Interestingly, a good yield was obtained when methyl-
sulfonyl-substituted amide 2g was employed as a part-
ner in the reaction of substrate 1a (77% yield,
Table 2, entry 12). The yield was decreased signifi-
cantly for the reaction of substrate 1a with N-allyl-
P,P-diphenylphosphinic amide 2h (35%, Table 2,
entry 13). No reaction occurred between compound
1a and N-allylbenzamide 2i under the standard condi-
tions (Table 2, entry 14). Substrates 1d and 1f reacted
smoothly with 3-phenylprop-2-en-1-amide 2c to fur-
nish the expected indolines (Table 2, entries 15 and
16).
6
H, Ts (2a)
30 (3f)
7
8
9
10
11
1a
1a
1a
1a
1a
CH3, Ts (2b)
C6H5, Ts (2c)
H, PhSO2 (2d)
H, 4-BrC6H4SO2 (2e) 65 (3j)
H, 4-NO2C6H4SO2
(2f)
H, Ms (2g)
H, Ph2PO (2h)
H, PhCO (2i)
C6H5, Ts (2c)
C6H5, Ts (2c)
60 (3g)
75 (3h)
68 (3i)
trace
12
13
14
15
16
1a
1a
1a
1d
1f
77 (3k)
35 (3l)
NR
65 (3m)
55 (3n)
[a]
Isolated yield N-allylsulfonamide 2.
To investigate whether the copper catalyst and
the scope of this tandem reaction. The reaction pro- ligand affect the post-Ullmann aza-Claisen rearrange-
ceeded smoothly when 1-(bromoethynyl)-2-(cyclopro- ment and 6p-electrocyclization, a control experiment
pylidenemethyl)benzene 1b was reacted with N-allyl- was performed (Scheme 2). The reaction of com-
4-methylbenzenesulfonamide 2a under the standard pound A1 (isolated from the Ullmann coupling step)
conditions, affording the desired product 3b in 66% was carried out under the standard conditions shown
yield (Table 2, entry 2). The structure of compound in Table 2 or in the absence of copper catalyst and
3b was unambiguously confirmed by X-ray crystallog- ligand. The results of both reactions were similar, in-
raphy analysis (Figure 1, see also the Supporting In- dicating that the copper catalyst and ligand are only
À
formation). Reactions of N-allyl-4-methylbenzenesul- involved in C N bond formation.
fonamide 2a and substrates 1 with electron-withdraw-
To get more insight into the experimental results,
ing groups attached to the aromatic ring gave satisfac- DFT calculations were performed for the last step
Adv. Synth. Catal. 2012, 354, 3087 – 3094
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Conclusions
In summary, we have developed a novel route for the
generation of fused indolines via a copper(II)-cata-
lyzed tandem reaction of 1-bromoethynyl-2-(cyclopro-
pylidenemethyl)arenes with allylic sulfonamides. The
transformation is a four-step cascade involving Ull-
mann coupling, aza-Claisen rearrangement, 6p-elec-
trocyclization, and intramolecular rearrangement.
Further exploration of 1-(bromoethynyl)-2-(cyclopro-
pylidenemethyl)arenes for other transformations is
ongoing.
Scheme 2. A control experiment for the reaction of com-
pound A1.
(from C to 3 in the proposed mechansim) with the
Gaussian 09 program package at B3LYP/6-31+G-
ACHTUNGTRENNUNG
(d,p) level.[14,15] The full geometry optimization of all
Experimental Section
minima and transition states involved was performed
at the chosen level of theory. Frequency calculations
were carried out at the same level of theory to identi-
fy all of the stationary points as minima (zero imagi-
nary frequencies) or first-order saddle points (one
imaginary frequency). The intrinsic reaction coordi-
nate (IRC)[16] pathways have been traced to verify
two desired minima connected by the transition
states.
General Experimental Procedure for the Copper-
Catalyzed Tandem Reaction of 1-(Bromoethynyl)-2-
(cyclopropylidenemethyl)arene 1 with N-Allyl-
sulfonamide 2
N-Allylsulfonamide 2 (0.3 mmol) was added to a solution of
1-(bromoethynyl)-2-(cyclopropylidenemethyl)arene
(0.36 mmol, 1.2 equiv.), CuACTHNUTRGNE(UNG OAc)2 (5.4 mg, 0.03 mmol), 1,10-
phenanthroline (11.0 mg, 0.06 mmol), and K2CO3 (83.0 mg,
0.6 mmol) in DMF (1.5 mL). The mixture was stirred at
1108C overnight under N2. After completion of reaction as
Solvent effects have been considered at the same
DFT level by reoptimizing the structures obtained in
the gas-phase using a simple self-consistent reaction indicated by TLC, the reaction mixture was cooled to room
field (SCRF) method[17–19] based on the polarizable
temperature. The mixture was filtered through Celite, and
continuum model (PCM)[20–22] with UFF cavities.[23]
diluted with ethyl acetate (30 mL). The organic solution was
washed with water (20 mLꢃ3), brine (30 mL), and dried
over Na2SO4. The solvent was evaporated and the residue
was purified by column chromatography on silica gel (eluted
with n-hexane/EtOAc=30:1 to 10:1) to provide the corre-
sponding product 3.
Our computations show that the dihedral angle (C-
À
À
À
8 C-9 C-5 C-4) between the 3-membered ring in
compound C and the adjacent 6-membered ring is
105.58. While in the TS and product 3, the corre-
sponding angles are 72.88 and 16.48, respectively. The
structure of TS is more similar with that of C. On the
other hand, the energy of TS is higher than that of C
9-Allyl-6-methyl-1-tosyl-2,3-dihydro-1H-benzo[f]indole
(3a): yield: 73%; 1H NMR (400 MHz, CDCl3): d=2.23 (t,
J=7.2 Hz, 2H), 2.36 (s, 3H), 2.49 (s, 3H), 4.01 (t, J=7.2 Hz,
and product 3 by 23.2 and 78.0 kcalmolÀ1, respective- 2H), 4.28 (d, J=4.8 Hz, 2H), 5.05–5.12 (m, 2H), 6.03–6.13
À
(m, 1H), 7.09 (d, J=8.0 Hz, 2H), 7.16–7.25 (m, 1H), 7.23–
7.36 (m, 4H), 7.47 (s, 1H), 8.06 (d, J=8.4 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=21.5, 21.6, 28.9, 33.8, 52.9,
115.4, 121.5, 125.8, 127.2, 127.8, 127.8, 128.3, 129.1, 129.4,
129.5, 131.0, 133.5, 135.0, 135.3, 136.2, 138.0, 138.7, 144.1;
HR-MS (ESI); m/z=400.1320, calcd. for C23H23NO2S (M+
Na+): 400.1347.
9-Allyl-1-tosyl-2,3-dihydro-1H-benzo[f]indole (3b): yield:
66%; 1H NMR (400 MHz, CDCl3): d=2.25 (t, J=6.8 Hz,
2H), 2.36 (s, 3H), 4.01 (t, J=6.8 Hz, 2H), 4.30 (d, J=
ly. The N-7 C-8 distance in TS (2.571 ꢂ) is more
close to that in C (2.793 ꢂ) rather than 3 (1.499 ꢂ).
All these data reveal that the TS is an early transition
state. At the same time, this process is a concerted in-
tramolecular rearrangement, which can proceed
smoothly with the barrier height being 23.2 kcalmolÀ1
in DMF at 1108C. Moreover, NBO analysis of TS
shows that C-8 and C-5 in TS are seen to have ap-
proximate valence configuration sp2 hybridization,
and there is a very clear interaction between lone pair 4.0 Hz, 2H), 5.06–5.12 (m, 2H), 6.06–6.09 (m, 1H), 7.10 (d,
J=8.0 Hz, 2H), 7.34–7.36 (m, 3H), 7.41–7.48 (m, 2H), 7.70
(d, J=7.2 Hz, 1H), 8.17 (d, J=8.0 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=21.7, 28.9, 33.9, 52.9, 115.5, 122.2,
125.6, 125.7, 125.9, 127.7, 128.1, 129.6, 132.8, 133.2, 135.0,
136.1, 137.9, 139.5, 144.2; HRMS (ESI): m/z=386.1175,
calcd. for C22H21NO2S (M+Na+): 386.1191.
(LP) natural bond orbital (NBO) of N atom and anti
lone pair (LP*) NBO of C-8, the stabilization energy
is 24.3 kcalmolÀ1. This means that this process is trig-
gered by the initial ring opening of 3-membered ring
attacking by lone pair, not p electron of the N atom.
9-Allyl-6-fluoro-1-tosyl-2,3-dihydro-1H-benzo[f]indole
(3c): yield: 65%; 1H NMR (400 MHz, CDCl3): d=2.25 (t,
J=6.8 Hz, 2H), 2.36 (s, 3H), 4.00 (t, J=6.8 Hz, 2H), 4.25 (s,
2H), 5.05–5.09 (m, 2H), 6.01–6.06 (m, 1H), 7.11 (d, J=
7.2 Hz, 2H), 7.21–7.35 (m, 5H), 8.12–8.16 (m, 1H);
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Synthesis of Benzoindolines via a Copper-Catalyzed Reaction
13C NMR (100 MHz, CDCl3): d=21.6, 28.9, 34.0, 52.9, 111.2
2H), 4.27 (d, J=4.0 Hz, 2H), 5.06–5.12 (m, 2H), 6.06–6.09
(m, 1H), 7.27–7.32 (m, 4H), 7.46–7.54 (m, 4H), 8.06 (d, J=
8.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=21.5, 28.8,
33.8, 52.9, 115.5, 121.6, 125.8, 127.2, 127.7, 127.8, 128.9,
129.4, 131.0, 133.2, 133.5, 135.4, 136.0, 137.8, 138.0, 138.6;
HR-MS (ESI): m/z=386.1163, calcd. for C22H21NO2S (M+
Na+): 386.1191.
9-Allyl-1-(4-bromophenylsulfonyl)-6-methyl-2,3-dihydro-
1H-benzo[f]indole (3j): yield: 65%; 1H NMR (400 MHz,
CDCl3): d=2.29 (t, J=6.8 Hz, 2H), 2.49 (s, 3H), 4.02 (t, J=
6.8 Hz, 2H), 4.24 (s, 2H), 5.06–5.10 (m, 2H), 6.04–6.07 (m,
1H), 7.24–7.32 (m, 4H), 7.43–7.48 (m, 3H), 8.05 (d, J=
8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=21.5, 28.9,
33.8, 52.9, 115.6, 121.8, 125.8, 127.3, 128.0, 128.4, 129.2,
129.5, 131.0, 132.2, 133.5, 135.6, 135.6, 136.9, 137.8, 138.3;
HR-MS (ESI): m/z=464.0275, calcd. for C22H20BrNO2S
(M+Na+): 464.0296.
9-Allyl-6-methyl-1-(methylsulfonyl)-2,3-dihydro-1H-ben-
zo[f]indole (3k): yield: 77%; 1H NMR (400 MHz, CDCl3):
d=2.48 (s, 3H), 2.78 (s, 3H), 3.17 (t, J=6.4 Hz, 2H), 4.09
(d, J=4.0 Hz, 2H), 4.14 (t, J=6.8 Hz, 2H), 5.01–5.04 (m,
2H), 5.95–5.99 (m, 1H), 7.29 (d, J=8.4 Hz, 1H), 7.52–7.53
(m, 2H), 7.98 (d, J=8.4 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=21.4, 30.0, 33.5, 37.4, 53.3, 115.5, 122.2, 125.6,
127.2, 128.0, 128.9, 131.0, 133.5, 135.1, 135.5, 137.7, 138.2;
HR-MS (ESI): m/z=324.1039, calcd. for C17H19NO2S (M+
Na+): 324.1034.
9-Allyl-1-(diphenylphosphoryl)-6-methyl-2,3-dihydro-1H-
benzo[f]indole (3l): yield: 35%; 1H NMR (400 MHz,
CDCl3): d=2.43 (s, 3H), 2.84 (t, J=6.8 Hz, 2H), 3.66–3.72
(m, 2H), 3.80 (d, J=4.8 Hz, 2H), 4.73–4.80 (m, 2H), 5.58–
5.65 (m, 1H), 7.18 (d, J=8.4 Hz, 1H), 7.40–7.41 (m, 8H),
7.70–7.76 (m, 5H); 13C NMR (100 MHz, CDCl3): d=21.3,
30.6, 33.4, 53.0 (d, JP, C =3.8 Hz), 114.9, 121.5, 122.4, 124.9,
2
2
(d, JCF =20.1 Hz), 115.5 (d, JC,F =23.8 Hz), 115.7, 121.5 (d,
4JC,F =4.8 Hz), 127.7, 128.4 (d, 3JC,F =8.6 Hz), 129.6, 129.8,
134.2 (d, 3JC,F =8.6 Hz), 134.8, 137.6, 137.7, 139.1, 139.1,
144.3, 160.6 (d, 1JC,F =244.0 Hz); HR-MS (ESI): m/z=
404.1105, calcd. for C22H20FNO2S (M+Na+): 404.1096.
9-Allyl-7-fluoro-1-tosyl-2,3-dihydro-1H-benzo[f]indole
(3d): yield: 70%; 1H NMR (400 MHz, CDCl3): d=2.26 (t,
J=6.4 Hz, 2H), 2.36 (s, 3H), 4.00 (t, J=6.4 Hz, 2H), 4.21
(d, J=4.0 Hz, 2H), 5.08–5.12 (m, 2H), 6.03–6.06 (m, 1H),
7.11 (d, J=7.6 Hz, 2H), 7.17–7.21 (m, 1H), 7.34–7.36 (m,
3H), 7.65–7.68 (m, 1H), 7.78 (d, J=11.6 Hz, 1H); 13C NMR
2
(100 MHz, CDCl3): d=21.6, 28.8, 34.0, 52.9, 109.9 (d, JC,F
=
2
21.9 Hz), 115.7 (d, JC,F =24.8 Hz), 115.9, 122.1, 127.7, 128.9
(d, JC,F =5.7 Hz), 129.6, 130.1, 130.2 (d, JC,F =8.6 Hz), 134.1
4
3
3
4
(d, JC,F =8.7 Hz), 134.9, 135.5 (d, JC,F =1.9 Hz), 137.4, 140.5,
144.3, 160.6 (d, 1JC,F =243.1 Hz); HR-MS (ESI): m/z=
404.1115, calcd. for C22H20FNO2S (M+Na+): 404.1096.
9-Allyl-6-chloro-1-tosyl-2,3-dihydro-1H-benzo[f]indole
(3e): yield: 66%; 1H NMR (400 MHz, CDCl3): d=2.25 (t,
J=6.8 Hz, 2H), 2.36 (s, 3H), 4.00 (t, J=6.8 Hz, 2H), 4.24 (s,
2H), 5.04–5.07 (m, 2H), 6.00–6.04 (m, 1H), 7.10 (d, J=
7.2 Hz, 2H), 7.26 (s, 1H), 7.33 (d, J=7.2 Hz, 2H), 7.39 (d,
J=8.8 Hz, 1H), 7.65 (s, 1H), 8.08 (d, J=8.8 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=21.6, 28.9, 33.8, 52.8, 115.8,
121.3, 126.3, 126.7, 127.6, 127.7, 129.6, 129.7, 131.2, 131.6,
134.0, 134.8, 137.6, 139.8, 144.4; HR-MS (ESI): m/z=
420.0779, calcd. for C22H20ClNO2S (M+Na+): 420.0801.
4-Allyl-5-tosyl-6,7-dihydro-5H-thieno
G
(3f):
yield: 30%; 1H NMR (400 MHz, CDCl3): d=2.19 (t, J=
6.4 Hz, 2H), 2.37 (s, 3H), 4.01 (t, J=6.4 Hz, 2H), 4.13 (d,
J=5.2 Hz, 2H), 5.08–5.12 (m, 2H), 6.05–6.09 (m, 1H), 7.12
(d, J=7.2 Hz, 2H), 7.34–7.41 (m, 4H), 7.53 (d, J=5.2 Hz,
1H); 13C NMR (100 MHz, CDCl3): d=21.6, 29.0, 35.3, 53.3,
115.7, 116.4, 123.5, 126.0, 127.8, 128.9, 129.5, 134.7, 135.1,
137.4, 138.5, 138.9, 139.7, 144.1; HR-MS (ESI): m/z=
392.0730, calcd. for C20H19NO2S2 (M+Na+): 392.0755.
127.0, 127.4, 128.6 (d, JP, C =12.4 Hz), 131.0, 132.1 (d, JP, C
125.8 Hz), 132.2 (d, JP, C =22.8 Hz), 132.2, 133.7, 135.7 (d,
P, C =3.8 Hz), 137.3, 141.8; 31P NMR (100 MHz, CDCl3): d=
=
J
9-(But-3-en-2-yl)-6-methyl-1-tosyl-2,3-dihydro-1H-benzo-
[f]indole (3g): yield: 60%; H NMR (400 MHz, CDCl3): d=
28.7; HR-MS (ESI): m/z=446.1661, calcd for C28H26NOP
1
(M+Na+): 446.1650.
1.65 (d, J=6.8 Hz, 3H), 2.14–2.32 (m, 2H), 2.36 (s, 3H),
2.47 (s, 3H), 3.94–4.06 (m, 2H), 4.91 (s, 1H), 5.21–5.28 (m,
2H), 6.47–6.54 (m, 1H), 7.10 (d, J=7.2 Hz, 2H), 7.23–7.26
(m, 2H), 7.36 (d, J=7.2 Hz, 2H), 7.46 (s, 1H), 8.29 (d, J=
8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=18.7, 21.4,
21.7, 29.0, 37.9, 53.0, 112.8, 121.8, 127.0, 127.0, 127.5, 127.8,
129.5, 130.2, 134.2, 135.0, 135.0, 135.1, 136.1, 138.5, 144.0,
144.1; HR-MS (ESI): m/z=414.1474, calcd. for C24H25NO2S
(M+Na+): 414.1504.
7-Fluoro-9-(1-phenylallyl)-1-tosyl-2,3-dihydro-1H-benzo-
[f]indole (3m): yield: 65%; H NMR (400 MHz, CDCl3): d=
1
2.26–2.30 (m, 2H), 2.39 (s, 3H), 4.00–4.13 (m, 2H), 5.25–
5.27 (m, 2H), 6.24 (d, J=6.4 Hz, 1H), 6.52–6.56 (m, 1H),
7.10–7.20 (m, 4H), 7.26–7.29 (m, 2H), 7.34–7.35 (m, 2H),
7.42–7.46 (m, 4H), 7.63–7.67 (m, 1H); 13C NMR (100 MHz,
CDCl3): d=21.7, 29.1, 50.0, 53.2, 112.1 (d, 2JC,F =22.9 Hz),
115.7 (d, 2JC,F =24.7 Hz), 118.0, 123.0, 126.1, 127.8, 128.1,
3
4
128.2, 129.7, 130.3 (d, JC,F =9.5 Hz), 130.9, 132.0 (d, JC,F
=
=
4
6-Methyl-9-(1-phenylallyl)-1-tosyl-2,3-dihydro-1H-benzo-
5.7 Hz), 132.7(d, 3JC,F=9.6 Hz), 135.1, 135.7 (d, JC,F
1.9 Hz), 138.9, 141.7, 142.2, 144.4, 159.7 (d, JC,F =243.1 Hz);
HR-MS (ESI): m/z=480.1427, calcd. for C28H24FNO2S (M+
Na+): 480.1409.
1
1
[f]indole (3h): yield: 75%; H NMR (400 MHz, CDCl3): d=
2.21–2.35 (m, 2H), 2.39 (s, 3H), 2.42 (s, 3H), 3.98–4.16 (m,
2H), 5.25–5.34 (m, 2H), 6.26 (d, J=7.2 Hz, 1H), 6.53–6.60
(m, 1H), 7.06 (d, J=8.4 Hz, 1H), 7.11–7.21 (m, 3H), 7.23–
7.30 (m, 2H), 7.36–7.40 (m, 3H), 7.43–7.50 (m, 3H), 7.71 (d,
J=8.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=21.4, 21.7,
29.2, 50.2, 53.2, 117.7, 122.5, 125.8, 127.1, 127.5, 127.8, 127.9,
128.1, 128.2, 129.6, 129.7, 132.4, 134.3, 135.1, 135.2, 136.4,
139.6, 140.0, 143.0, 144.2; HR-MS (ESI): m/z=476.1663,
calcd. for C29H27NO2S (M + Na+): 476.1660.
4-(1-Phenylallyl)-5-tosyl-6,7-dihydro-5H-thienoACTHNUGTRNEUNG[2,3-f]-
indole (3n): yield: 55%; 1H NMR (400 MHz, CDCl3): d=
2.18–2.29 (m, 2H), 2.39 (s, 3H), 4.01–4.11 (m, 2H), 5.24–
5.30 (m, 2H), 6.14 (d, J=6.8 Hz, 1H), 6.35–6.42 (m, 1H),
7.01 (d, J=4.8 Hz, 1H), 7.16–7.20 (m, 4H), 7.26–7.29 (m,
2H), 7.36 (d, J=7.2 Hz, 2H), 7.43–7.45 (m, 3H); 13C NMR
(100 MHz, CDCl3): d=21.7, 29.2, 50.2, 53.5, 117.1, 117.5,
125.0, 125.5, 126.0, 127.9, 128.0, 128.4, 129.6, 132.3, 134.8,
135.3, 138.3, 139.1, 139.3, 140.0, 142.5, 144.2; HR-MS (ESI):
m/z=468.1042, calcd. for C26H23NO2S2 (M+Na+): 468.1068.
9-Allyl-6-methyl-1-(phenylsulfonyl)-2,3-dihydro-1H-ben-
zo[f]indole (3i): yield: 68%; 1H NMR (400 MHz, CDCl3):
d=2.21 (t, J=6.8 Hz, 2H), 2.48 (s, 3H), 4.02 (t, J=6.8 Hz,
Adv. Synth. Catal. 2012, 354, 3087 – 3094
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3091

Shaoyu Li et al.
FULL PAPERS
N-Allyl-N-{[2-(cyclopropylidenemethyl)-4-methylphenyl]-
ethynyl}-4-methylbenzenesulfonamide (A1): yield: 80%;
1H NMR (400 MHz, CDCl3): d=1.17 (t, J=8.0 Hz, 2H),
1.41 (t, J=8.0 Hz, 2H), 2.32 (s, 3H), 2.43 (s, 3H), 4.07 (d,
J=6.0 Hz, 2H), 5.22–5.32 (m, 2H), 5.77–5.82 (m, 1H), 6.93
(d, J=7.6 Hz, 1H), 7.11 (s, 1H), 7.22 (d, J=8.0 Hz, 1H),
7.32 (d, J=7.6 Hz, 2H), 7.59 (s, 1H), 7.85 (d, J=7.6 Hz,
2H); 13C NMR (100 MHz, CDCl3): d=0.6, 4.3, 21.7, 25.6,
54.5, 69.6, 85.6, 116.4, 118.3, 120.1, 120.2, 125.7, 125.7, 127.4,
127.8, 127.9, 129.8, 131.1, 132.1, 134.8, 137.8, 139.1, 144.7;
HR-MS (ESI): m/z=400.1367, calcd. for C23H23NO2S (M+
Na+): 400.1347.
Crystallographic data for the structure 3b have been de-
posited with the Cambridge Crystallographic Data Centre as
supplementary publication no. CCDC 876411. These data
can be obtained free of charge from The Cambridge Crystal-
lographic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif or on application to CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK [fax (internat.): +44-1223/336-033; e-
mail: deposit@ccdc.cam.ac.uk.
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Supporting Information
Experimental procedures, characterization data, 1H and
13C NMR spectra of compounds 1 and 3, and a CIF file of
compound 3b are available in the Supporting Information.
Acknowledgements
Financial support from National Natural Science Foundation
of China (Nos. 21032007 and 21172038) is gratefully ac-
knowledged. We thank Dr. Jason Wong (Roche Pharma Re-
search and Early Development, China) for English review.
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