Catalytic C-2 Allylation of Indoles by Electronic Modulation of the Indole Ring and its Application to the Synthesis of Functionalized Carbazoles

Article abstract of DOI:10.1002/adsc.201600568

We report a palladium-catalyzed C-2 allylation of indoles and subsequent cyclization of the allylated indoles. The electronic effects of chloro and ester groups that can be readily installed at the C-3 position of indoles facilitated a highly efficient C–H allylation at the C-2 position. The resulting 2-allyl-3-chloroindoles were found to be suitable substrates for benzannulation reactions with alkynes and norbornadiene as an acetylene synthon. This approach, utilizing readily available indoles, allyl acetates, and norbornadiene, allows a rapid access to complex carbazoles. (Figure presented.).

Full text of DOI:10.1002/adsc.201600568

UPDATES
DOI: 10.1002/adsc.201600568
Catalytic C-2 Allylation of Indoles by Electronic Modulation of
the Indole Ring and its Application to the Synthesis of Function-
alized Carbazoles
Ju Young Lee,a Hyeri Ha,a Seri Bae,a Inhyuk Han,a and Jung Min Jooa,*
a
Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University, Busan 46241,
Republic of Korea
E-mail: jmjoo@pusan.ac.kr
Received: May 31, 2016; Revised: July 15, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600568.
Abstract: We report a palladium-catalyzed C-2 ally-
lation of indoles and subsequent cyclization of the
allylated indoles. The electronic effects of chloro
and ester groups that can be readily installed at the
C-3 position of indoles facilitated a highly efficient
C–H allylation at the C-2 position. The resulting 2-
allyl-3-chloroindoles were found to be suitable sub-
strates for benzannulation reactions with alkynes
and norbornadiene as an acetylene synthon. This
approach, utilizing readily available indoles, allyl
acetates, and norbornadiene, allows a rapid access
to complex carbazoles.
lectivity was achieved, only two types of directing
groups, the 2-pyrimidyl and N,N-dialkylcarbamoyl
groups, have proven effective. Moreover, the substitu-
ents at the C-3 position significantly hindered the di-
recting group-assisted allylation.[12]
We postulated that modification of the electronic
nature of the electron-rich indole ring with electron-
withdrawing groups (EWGs) could promote the C-2
allylation of indoles.[13] Based on our recent results in
the C–H alkylation of pyrazoles, we surmised that the
Keywords: allylation; annulation; carbazoles; in-
doles; palladium
Introduction
Indole is an important heterocyclic core, frequently
found in natural products and pharmaceuticals.[1] In
the past decade, much progress has been made to-
wards the functionalization of indoles by directly in-
stalling the desired functional group in the heterocy-
clic ring.[2–5] Particularly, direct C–H allylation reac-
tions facilitate the synthesis of allylated indoles, a key
structural motif in many natural products.[6] Further-
more, owing to the facile transformation of the allyl
group into various functional groups, the catalytic al-
lylation strategy is useful for the synthesis of complex
indole compounds and annulated heterocycles.[7]
Consistent with the general reactivity of indoles, al-
lylation preferentially occurs at the C-3 position,
which is more nucleophilic than the C-2 position.[8–10]
To enable the C-2 selective allylation of indoles, a di-
recting group strategy has been developed previously
Figure 1. A: Directing group-assisted C-2-allylation of in-
doles. B: C-2 allylation enabled by the effect of electron-
withdrawing groups and subsequent cyclization to give car-
(Figure 1 A).[4g,h,11] Although the desired C-2-regiose- bazoles.
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Table 1. C-2 allylation of indoles by electronic modulation
electronic effect of appropriately positioned electron-
withdrawing groups should facilitate C–H allylation at
the indole C-2 position.[14] For example, a chloro
group installed at the indole C-3 position should
enable the formation of synthetically useful 2-allyl-3-
chloroindoles via C–H allylation (Figure 1 B). While
2-allyl-3-haloindoles have proven useful in the annu-
lation of indoles, their preparation relies on the cycli-
zation reactions of iodoanilines, rather than taking ad-
vantage of readily available indoles.[15] In addition,
only the annulation reactions of iodoindoles with al-
kynes have been examined until now, leaving open
the possibility that carbazoles with a variety of substi-
tution patterns could be synthesized from haloindoles
and unsaturated hydrocarbons.[16]
of the indole ring.[a]
Herein, we report the catalytic C–H allylation of in-
doles at the C-2 position in high yields. The chloro
and ester groups were utilized as electron-withdraw-
ing substituents. C–H allylation was carried out using
readily available functionalized allyl acetates.[17] In
the case of chloro substrates, the resulting 2-allyl-3-
chloroindoles were converted to carbazoles by se-
quential cyclization and isomerization reactions. In
addition to internal alkynes, norbornadiene can be
employed as an acetylene synthon in the retro-Diels–
Alder reaction.[18–20] This represents a new approach
to the synthesis of 2-alkylcarbazoles, where an allyl
group and norbornadiene merge to form a benzene
ring in the carbazole heterocycle.[21,22]
Results and Discussion
First, the electronic effects of electron-withdrawing
groups on C-2 allylation reactions of indoles were
evaluated using a catalytic system derived from
Pd(OAc)2 and PPh3 (Table 1).[23] We propose that the
C-2 allylation of indoles occurs via p-allyl palladium
complexes, similar to the C–H allylation of electron-
deficient arenes (see the Supporting Information for
the proposed mechanism).[24] N-Methylindole 1a did
not produce appreciable amounts of either the C-2 al-
lylation product 2a or the corresponding C-3 allyla-
tion product (entry 1). An electron-withdrawing
group attached to the nitrogen atom had a positive
impact on the allylation; the reactions of N-tosylin-
dole 1b and carbamoylindole 1c produced the corre-
sponding C-2 allylation products 2b and 2c in 11%
and 18% yields, respectively (entries 2 and 3). The
formation of the corresponding C-3 allylation prod-
ucts was not observed in these cases. The low yield of
[a]
Reaction conditions: indole (0.40 mmol), allyl acetate
(0.60 mmol), Pd(OAc)2 (5 mol%), PPh3 (20 mol%),
K2CO3 (1.0 mmol), toluene (0.40M), 1208C, 14 h.
The reaction was carried out for 36 h to ensure complete
consumption of the starting material.
The reaction was carried out at 1308C.
[b]
[c]
2c suggests that the N,N-dimethylcarbamoyl group is of C-2 allylation (entry 4). Crucially, when a chloro
not an efficient directing group in the Pd-catalyzed re- substituent was attached to the indole C-3 position,
action, in contrast to its strong effect in the Rh-cata- the allylation product 2e was obtained in almost
lyzed reactions.[11c] In addition, the low yield of the 3- quantitative yield (entry 5). Common indole protect-
methyl variant 1d indicates that simply blocking the ing groups, namely benzenesulfonyl and N,N-
C-3 position does not considerably increase the yield dimethylACTHUNRTGNEaGNU minosulfamoyl, were tolerated in the reac-
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tion (entries 6 and 7). Furthermore, a series of experi- chloro and ester groups gave low yields of allylation
ments using 3-carboxylate counterparts 1h–1m re- products, showing the importance of the fine balance
vealed that the ester group too promoted the C–H al- of the electronic effects in Pd-catalyzed C–H func-
lylation of indoles, but to a lesser extent than the tionalization reactions.[25] When N-tosylated 3-nitroin-
chloro group (entries 8–13). These results show that dole 1n was subjected to the reaction conditions, it
in the allylation reactions of indole-3-carboxylates, underwent deprotection followed by N-allylation, fur-
the electronic effect of protecting groups at N-1 is not nishing 3 as the major product (entry 14).
as significant as the effect exerted by the ester group
The C-2 selective allylation worked well for indoles
at C-3. The reactions of indoles possessing other car- bearing electron-donating and electron-withdrawing
bonyl groups, such as formyl and acetyl groups, were substituents on the benzene ring (Table 2). Alkoxy,
not efficient because of an olefin isomerization reac- cyano, nitro and chloro groups were compatible with
tion of the allylation products (Table S2 in the Sup- the allylation conditions (entries 1–5). Notably, an
porting Information). However, functional groups azaindole derivative 1t was allylated to generate the
that are either less electron-withdrawing (Br, I) or corresponding product 2t in 89% yield (entry 6). Both
more electron-withdrawing (CN, NO2) than the cinnamyl acetate and its regioisomeric secondary ace-
Table 2. Scope of the C–H allylation of 3-chloroindoles.[a]
[a]
Reaction conditions: indole (0.40 mmol), allyl acetate (0.60 mmol), Pd(OAc)2 (5 mol%), PPh3 (20 mol%), K2CO3
(1.0 mmol), toluene (0.40M), 1208C, 14 h.
The reaction was carried out for 42 h to ensure complete consumption of the starting material.
The reaction was carried out with cinnamyl acetate.
[b]
[c]
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tate gave the linear isomer 4a, consistent with the re- a tandem sequence of these reactions to eventually
sults obtained in the allylation of pyrazoles form the carbazole 6a. The annulation with norborna-
(entry 7).[14a] Therefore, depending on the preparation diene was efficient in both 1,4-dioxane and toluene
method preferred for allyl acetates, either primary or (77% and 72% yields, respectively). In agreement
secondary acetates could be used for the C-2 allyla- with previous studies using norbornadiene, the follow-
tion of indoles. Several allyl aryl acetates were com- ing characteristics were observed: (i) an excess of nor-
petent allyl group donors and afforded 4b–4e in good bornadiene was essential for high efficiency; presuma-
to high yields (entries 8–11). Also, the reaction of bly it increases complexation with the Pd complexes
azaindole 1t and cinnamyl acetate resulted in the syn- and prevents additional reactions with the remaining
thesis of 4f in 83% yield.
strained olefinic portion of the cyclized product (see
After establishing a general method to afford 2- the Supporting Information for details); and (ii) the
allyl-3-chloroindoles, we examined their amenability retro-Diels–Alder reaction was better facilitated
to annulation reactions. Due to the lack of general ap- when the indole protecting group was removed.[19c]
proaches to prepare 2-allyl-3-chloroindoles, reactions
Using the two-step sequence, we synthesized a vari-
of these functionalized indoles were not investigated ety of carbazoles from 2-allyl-3-chloroindoles
earlier. In order to identify new two-carbon units that (Table 3). It is noteworthy that the newly formed car-
could undergo annulation reactions with 2-allyl-3- bazole benzene rings possess a methyl or benzyl sub-
chloroindoles, we first carried out a cyclization reac-
tion with norbornene (Scheme 1A). The formation of
Table 3. Synthesis of carbazoles by annulation with norbor-
cyclized product 5 illustrated that strained alkenes
could be viable partners for the annulation of 2-allyl-
3-chloroindoles. The diene counterpart, norborna-
diene has been used as an acetylene synthon, instead
of gaseous polymerizable acetylene, in Pd-catalyzed
annulation reactions.[19] We envisioned that the annu-
lation of 2-allyl-3-chloroindoles with norbornadiene,
followed by retro-Diels–Alder and isomerization re-
actions, should afford aromatized carbazole structures
(Scheme 1B). Gratifyingly, it was feasible to perform
nadiene as an acetylene synthon.[a]
[a]
Reaction conditions: 1) indole (0.20 mmol), norborna-
diene (1.2 mmol), Pd(OAc)2 (10 mol%), P(t-Bu)3HBF4
(22 mol%), Cs2CO3 (0.40 mmol), toluene (0.20M),
1308C, 14 h; 2) KOH (0.60 mmol), EtOH (0.20M), 808C,
14 h.
Scheme 1. Annulation of chloroindole 2e with norbornene
and norbornadiene.
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stituent at the C-2 position, which is difficult to intro- bazoles from indoles, and allows the systematic prepa-
duce using a convergent approach.[26] Alkoxy and ration of new, fused indole-containing compounds.
cyano groups were tolerated in the cyclization process
(6b–6d). Azaindole 2t was successfully transformed to
pyridoindole 6e. In addition to allyl-substituted in- Experimental Section
doles, cinnamyl-substituted indoles could also be used
for cyclization, ultimately furnishing 2-benzyl-substi- General Procedure A for the N-Protection of Indoles
tuted carbazoles (6f–6i).
Encouraged by these results, we further explored
the utility of 2-allyl-3-chloroindoles for the synthesis
To a stirred solution of the indole (1.0 equiv.) in THF (and/
or DMF) at 08C under a nitrogen atmosphere was added
60% sodium hydride in oil. After stirring for 20 min at 08C,
of highly substituted carbazoles. In light of the results
obtained by the Larock group, where a 2-allyl-3-io-
doindole reacted with internal alkynes to give carba-
zoles in moderate yields, we attempted the cyclization
of the chloro-substituted variant 2e (Scheme 2).[15a] In
the presence of Pd(OAc)2 and P(t-Bu)3HBF4, both
diaryl- and dialkylacetylenes led to the formation of
their corresponding carbazoles, 7a and 7b, in good
yields. This result suggests that 2-allyl-3-chloroindoles
can be alternatively employed in cyclization reactions
in place of their iodide counterparts.
a protecting reagent was added dropwise, and the resulting
mixture was stirred for 16 h at 258C. The reaction mixture
was treated with water (15 mL) and EtOAc (20 mL) and
transferred to a 125-mL separatory funnel. The organic
layer was collected, and the aqueous layer was extracted
with EtOAc (25 mLꢁ2). The combined organic layers were
washed with brine (20 mL), dried over sodium sulfate, and
filtered. The filtrate was concentrated, and the residue was
purified by flash column chromatography to afford the de-
sired indole.
General Procedure B for the C–H Allylation of
Indoles
To an 8-mL glass vial equipped with a magnetic stir bar
were sequentially added K2CO3 (138 mg, 1.0 mmol), the
indole substrate (0.40 mmol), allyl acetate (0.60 mmol), tolu-
ene (1.00 mL, 0.40M), Pd(OAc)2 (4.50 mg, 0.020 mmol) and
PPh3 (21.0 mg, 0.080 mmol). The reaction mixture was
purged with nitrogen through a Teflon-lined cap. Then, the
cap was replaced with a new Teflon-lined solid cap. The re-
action vial was moved to a preheated reaction block (120 or
1308C). After stirring for 14 h, the reaction mixture was
cooled to 258C and concentrated. The residue was purified
by flash column chromatography to provide the desired
product.
Scheme 2. Synthesis of carbazoles by annulation with inter-
nal alkynes.
Conclusions
General Procedure C for the Synthesis of Carbazoles
from 2-Allyl-3-chloroindoles
In conclusion, we have developed a catalytic C-2 ally-
lation reaction of indoles by taking advantage of elec-
tron-withdrawing groups at the C-3 position. The
chloro and ester groups that can be easily installed by
the electrophilic substitution of indoles, enabled ally-
lation at the C-2 position in a highly efficient manner,
providing an alternative to the directing group-assist-
ed C–H allylation reactions. This general approach
for the preparation of 2-allyl-3-chloroindoles facilitat-
To an 8-mL glass vial equipped with a magnetic stir bar
were sequentially added Cs2CO3 (130 mg, 0.40 mmol), the 2-
allyl-3-chloroindole substrate (0.20 mmol), norbornadiene
(122 mL, 1.2 mmol), toluene or 1,4-dioxane (1.00 mL,
0.20M), Pd(OAc)2 (4.50 mg, 0.020 mmol) and P(t-Bu)3HBF4
(12.8 mg, 0.044 mmol). The reaction mixture was purged
with nitrogen through a Teflon-lined cap. Then, the cap was
replaced with a new Teflon-lined solid cap. The reaction vial
was moved to a preheated reaction block (1308C). After
ed the development of new annulation reactions of in- stirring for 14 h, the reaction mixture was cooled to 258C
and filtered through a short pad of silica gel. The solvent
was evaporated, and the crude material was transferred to
an 8-mL glass vial. Then, EtOH (1.00 mL, 0.20M) and KOH
(33.7 mg, 0.60 mmol) were added. The reaction vial was
moved to a preheated reaction block (808C). After stirring
for 14 h, the reaction mixture was cooled to 258C. The reac-
tion mixture was treated with water (15 mL) and EtOAc
(20 mL) and transferred to a 125-mL separatory funnel. The
organic layer was collected and the aqueous layer was ex-
tracted with EtOAc (25 mLꢁ2). The combined organic
doles. 2-Allyl-3-chloroindoles were smoothly convert-
ed to the corresponding carbazoles by a Pd-catalyzed
cyclization with norbornadiene and alkynes. In the re-
action with norbornadiene, retro-Diels–Alder and iso-
merization reactions took place to furnish 2-methyl-
and 2-benzyl-substituted carbazoles. This result repre-
sents the first catalytic reaction between 2-allyl-3-
chloroindoles and a strained alkene to give carba-
zoles. This strategy based on C–H allylation comple-
ments the annulation methods for the synthesis of car- layers were washed with brine (20 mL), dried over sodium
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sulfate, and filtered. The filtrate was concentrated, and the
residue was purified by flash column chromatography to
afford the desired carbazole.
134.6, 127.6, 125.5, 123.4, 123.3, 119.0, 114.0, 111.5, 38.6;
HR-MS (ESI): m/z=259.0305, calcd. for C10H12ClN2O2S
[M+H]+: 259.0303.
1-Tosyl-1H-indole (1b):[27] Following the general proce-
dure A, 1H-indole (1.00 g, 8.54 mmol), THF (10.0 mL),
DMF (10.0 mL), 60% sodium hydride in oil (376 mg,
9.39 mmol), and 4-methylbenzene-1-sulfonyl chloride
(1.79 g, 9.39 mmol) were used. Flash column chromatogra-
phy (hexanes/EtOAc=9:1) provided indole 1b as a yellow
Methyl 1-methyl-1H-indole-3-carboxylate (1h):[32] Follow-
ing the general procedure A, methyl 1H-indole-3-carboxyl-
ate (3.00 g, 17.1 mmol), THF (25.0 mL), 60% sodium hy-
dride in oil (451 mg, 11.3 mmol), and iodomethane
(1.17 mL, 18.8 mmol) were used. Flash column chromatogra-
phy (hexanes/EtOAc=5:1) provided indole 1h as a white
1
1
solid; yield: 937 mg (40%). H NMR (300 MHz, CDCl3): d=
solid; yield: 1.58 g (49%). H NMR (300 MHz, CDCl3): d=
7.99 (dd, J=8.2, 0.7 Hz, 1H), 7.76 (d, J=8.3 Hz, 2H), 7.62–
7.45 (m, 2H), 7.36–7.28 (m, 1H), 7.25–7.14 (m, 3H), 6.65 (d,
J=3.6 Hz, 1H), 2.33 (s, 3H).
8.21–8.13 (m, 1H), 7.79 (s, 1H), 7.38–7.27 (m, 3H), 3.91 (s,
3H), 3.84 (s, 3H).
Methyl 1-tosyl-1H-indole-3-carboxylate (1i):[33] To a stirred
solution of methyl 1H-indole-3-carboxylate (1.00 g,
5.71 mmol), triethylamine (1.04 mL, 7.42 mmol) and DMAP
(27.9 mg, 0.228 mmol) in CH2Cl2 (20.0 mL) under a nitrogen
atmosphere was added 4-methylbenzene-1-sulfonyl chloride
(1.09 g, 5.71 mmol). The mixture was stirred for 14 h at
258C. The reaction mixture was treated with a saturated
aqueous solution of NaHCO3 (15 mL) and CH2Cl2 (20 mL)
and transferred to a 125-mL separatory funnel. The organic
layer was collected, and the aqueous layer was extracted
with CH2Cl2 (25 mLꢁ2). The combined organic layers were
washed with brine (20 mL), dried over sodium sulfate, and
filtered. The filtrate was concentrated, and the residue was
purified by flash column chromatography (hexanes/
EtOAc=6:1) to provide indole 1i as a white solid; yield:
890 mg (47%). 1H NMR (300 MHz, CDCl3): d=8.28 (s,
1H), 8.16–8.10 (m, 1H), 7.99–7.93 (m, 1H), 7.83 (d, J=
8.3 Hz, 2H), 7.41–7.27 (m, 4H), 3.93 (s, 3H), 2.36 (s, 3H).
Methyl 1-(phenylsulfonyl)-1H-indole-3-carboxylate (1j):[34]
Following the general procedure A, methyl 1H-indole-3-car-
boxylate (1.00 g, 5.71 mmol), THF (5.00 mL), DMF
(5.00 mL), sodium hydride 60% in oil (274 mg, 6.85 mmol),
and benzenesulfonyl chloride (0.729 mL, 5.71 mmol) were
used. Flash column chromatography (hexanes/EtOAc=6:1)
provided indole 1j as a white solid; yield: 1.15 g (64%).
1H NMR (300 MHz, CDCl3): d=8.28 (s, 1H), 8.17–8.10 (m,
1H), 8.00–7.92 (m, 3H), 7.60 (t, J=7.4 Hz, 1H), 7.49 (t, J=
7.5 Hz, 2H), 7.41–7.31 (m, 2H), 3.93 (s, 3H).
N,N-Dimethyl-1H-indole-1-carboxamide (1c):[28] Following
the general procedure A, 1H-indole (1.00 g, 8.54 mmol),
THF (10.0 mL), 60% sodium hydride in oil (376 mg,
9.39 mmol), and dimethylcarbamic chloride (0.865 mL,
9.39 mmol) were used. Flash column chromatography (hex-
anes/EtOAc=3:1) provided indole 1c as a pink solid; yield:
1
1.31 g (81%). H NMR (300 MHz, CDCl3): d=7.65 (d, J=
8.2 Hz, 1H), 7.60 (d, J=7.8 Hz, 1H), 7.32 (d, J=3.4 Hz,
1H), 7.31–7.26 (m, 1H), 7.20 (t, J=7.5 Hz, 1H), 6.60 (d, J=
3.5 Hz, 1H), 3.10 (s, 6H).
3-Methyl-1-tosyl-1H-indole (1d):[29] Following the general
procedure A, 3-methyl-1H-indole (1.00 g, 7.62 mmol), DMF
(10.0 mL), 60% sodium hydride in oil (335 mg, 8.38 mmol),
and 4-methylbenzene-1-sulfonyl chloride (1.60 g, 8.38 mmol)
were used. Flash column chromatography (hexanes/
EtOAc=18:1) provided indole 1d as a yellow solid; yield:
1
776 mg (36%). H NMR (300 MHz, CDCl3): d=7.98 (d, J=
8.2 Hz, 1H), 7.74 (d, J=8.3 Hz, 2H), 7.45 (d, J=7.4 Hz,
1H), 7.38–7.28 (m, 2H), 7.25–7.12 (m, 3H), 2.33 (s, 3H),
2.24 (s, 3H).
3-Chloro-1-tosyl-1H-indole (1e):[30] Following the general
procedure A, 3-chloro-1H-indole (615 mg, 4.06 mmol),
DMF (6.00 mL), 60% sodium hydride in oil (179 mg,
4.47 mmol), and 4-methylbenzene-1-sulfonyl chloride
(852 mg, 4.47 mmol) were used. Flash column chromatogra-
phy (hexanes/EtOAc=19:1) provided indole 1e as a white
1
solid; yield: 994 mg (80%). H NMR (300 MHz, CDCl3): d=
8.00 (d, J=8.2 Hz, 1H), 7.77 (d, J=8.4 Hz, 2H), 7.61–7.46
(m, 2H), 7.42–7.28 (m, 2H), 7.25–7.18 (m, 2H), 2.35 (s, 3H).
3-Chloro-1-(phenylsulfonyl)-1H-indole (1f):[31] Following
the general procedure A, 3-chloro-1H-indole (1.89 g,
12.5 mmol), THF (10.0 mL), 60% sodium hydride in oil
(548 mg, 13.7 mmol), and benzenesulfonyl chloride
(1.95 mL, 13.7 mmol) were used. Flash column chromatogra-
phy (hexanes/EtOAc=19:1) provided indole 1f as a white
Methyl 1-(N,N-dimethylsulfamoyl)-1H-indole-3-carboxyl-
ate (1k): Following the general procedure A, methyl 1H-
indole-3-carboxylate (5.00 g, 28.5 mmol), THF (10.0 mL),
DMF (10.0 mL), 60% sodium hydride in oil (1.37 g,
34.2 mmol), and dimethylsulfamoyl chloride (3.06 mL,
28.5 mmol) were used. Flash column chromatography (hex-
anes/EtOAc=6:1) provided indole 1k as a white solid;
yield: 7.20 g (89%); mp 96–988C. IR (film): n=3140, 2953,
1
solid; yield: 2.19 g (60%). H NMR (300 MHz, CDCl3): d=
1714, 1392, 1204, 1172 cmÀ1 1H NMR (300 MHz, CDCl3):
;
8.01 (d, J=8.3 Hz, 1H), 7.89 (d, J=7.2 Hz, 2H), 7.66–7.27
(m, 7H).
d=8.21 (dd, J=5.9, 3.2 Hz, 1H), 8.15 (s, 1H), 7.94 (dd, J=
6.2, 3.0 Hz, 1H), 7.42–7.33 (m, 2H), 3.94 (s, 3H), 2.89 (s,
6H); 13C NMR (75 MHz, CDCl3): d=164.4, 135.6, 133.0,
127.2, 125.1, 124.1, 122.0, 113.7, 111.5, 51.7, 38.6; HR-MS
(ESI): m/z=283.0750, calcd. for C12H15N2O4S [M+H]+:
283.0747.
Methyl 1-[(4-nitrophenyl)sulfonyl]-1H-indole-3-carboxyl-
ate (1l): Following the general procedure A, methyl 1H-
indole-3-carboxylate (1.00 g, 5.71 mmol), THF (10.0 mL),
60% sodium hydride in oil (320 mg, 7.99 mmol), and 4-nitro-
benzene-1-sulfonyl chloride (1.90 g, 8.57 mmol) were used.
Crystallization (hexanes/EtOAc) provided indole 1l as
a yellow solid; yield: 1.44 g (70%); mp 211–2138C. IR
3-Chloro-N,N-dimethyl-1H-indole-1-sulfonamide
(1g):
Following the general procedure A, 3-chloro-1H-indole
(1.00 g, 6.60 mmol), THF (10.0 mL), DMF (2.50 mL), 60%
sodium hydride in oil (343 mg, 8.58 mmol), and dimethylsul-
famoyl chloride (0.85 mL, 7.92 mmol) were used. Flash
column chromatography (hexanes/EtOAc=11:1) provided
indole 1g as a brown solid; yield: 0.76 g (45%); mp 105–
1088C. IR (film): n=3136, 1469, 1445, 1414, 1389, 1274,
1203 cmÀ1 1H NMR (300 MHz, CDCl3): d=7.95 (d, J=
;
8.3 Hz, 1H), 7.63 (d, J=6.9 Hz, 1H), 7.45 (s, 1H), 7.42–7.32
(m, 2H), 2.85 (s, 6H); 13C NMR (75 MHz, CDCl3): d=
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(film): n=3105, 1717, 1534, 1404, 1387, 1349, 1201 cmÀ1
;
CDCl3): d=146.4, 139.6, 136.1, 133.3, 131.4, 128.9, 128.6,
128.3, 128.0, 127.3, 124.9, 124.7, 123.8, 111.7, 111.6, 108.9,
1H NMR (300 MHz, CDCl3): d=8.33 (d, J=8.9 Hz, 2H),
8.24 (s, 1H), 8.19–8.09 (m, 3H), 7.96 (d, J=7.6 Hz, 1H),
7.47–7.34 (m, 2H), 3.94 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=163.8, 151.0, 142.9, 134.8, 131.6, 128.5, 128.0,
126.2, 125.2, 124.9, 122.7, 115.2, 113.2, 52.0; HR-MS (ESI):
m/z=361.0485, calcd. for C16H13N2O6S [M+H]+: 361.0489.
70.8;
HR-MS
(ESI):
m/z=398.0612,
calcd.
for
C21H17ClNO3S [M+H]+: 398.0612.
3-Chloro-1-(phenylsulfonyl)-1H-indole-4-carbonitrile (1q):
Following the general procedure A, 3-chloro-1H-indole-4-
carbonitrile (1.01 g, 5.70 mmol), THF (5.00 mL), DMF
(5.00 mL), 60% sodium hydride in oil (228 mg, 5.70 mmol),
and benzenesulfonyl chloride (0.73 mL, 5.70 mmol) were
used. Crystallization (hexanes/EtOAc) provided indole 1q
as a white solid; yield: 1.28 g (71%); mp 119–1208C. IR
Methyl
1-(dimethylcarbamoyl)-1H-indole-3-carboxylate
(1m): Following the general procedure A, methyl 1H-
indole-3-carboxylate (1.00 g, 5.71 mmol), THF (10.0 mL),
60% sodium hydride in oil (251 mg, 6.28 mmol), and dime-
thylcarbamic chloride (0.578 mL, 6.28 mmol) were used.
Flash column chromatography (hexanes/EtOAc=2:1) pro-
vided indole 1m as a white solid; yield: 1.23 g (87%); mp
115–1178C. IR (film): n=3138, 3072, 3025, 2956, 2851, 1682,
1
(film): n=3145, 3125, 2231, 1417, 1379, 732 cmÀ1; H NMR
(300 MHz, CDCl3): d=8.26 (d, J=8.4 Hz, 1H), 7.90 (d, J=
7.8 Hz, 2H), 7.72 (s, 1H), 7.62 (t, J=8.4 Hz, 2H), 7.57–7.39
(m, 3H); 13C NMR (75 MHz, CDCl3): d=137.2, 134.9, 134.3,
130.3, 129.8, 127.5, 127.0, 125.7, 125.4, 118.3, 116.3, 112.6,
1209 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.23–8.14 (m,
;
1H), 8.01 (s, 1H), 7.67–7.58 (m, 1H), 7.40–7.29 (m, 2H),
3.93 (s, 3H), 3.12 (s, 6H); 13C NMR (75 MHz, CDCl3): d=
164.8, 153.6, 135.8, 132.2, 126.6, 124.5, 123.3, 121.8, 113.4,
110.8, 51.4, 38.4; HR-MS (ESI): m/z=247.1079, calcd. for
C13H15N2O3 [M+H]+: 247.1077.
3-Nitro-1-tosyl-1H-indole (1n): Following the general pro-
cedure A, 3-nitro-1H-indole (300 mg, 1.85 mmol), DMF
(5.00 mL), 60% sodium hydride in oil (88.8 mg, 22.2 mmol),
103.6; HR-MS (ESI): m/z=338.9967, calcd.
for
C15H9ClN2NaO2S [M+Na]+: 338.9965.
3-Chloro-5-nitro-1-(phenylsulfonyl)-1H-indole (1r): Fol-
lowing the general procedure A, 3-chloro-5-nitro-1H-indole
(725 mg, 3.69 mmol), THF (5.00 mL), DMF (5.00 mL), 60%
sodium hydride in oil (177 mg, 4.43 mmol), and benzenesul-
fonyl chloride (0.5 mL, 3.69 mmol) were used. Crystalliza-
tion (hexanes/EtOAc) provided indole 1r as a beige solid;
yield: 471 mg (38%); mp 199–2018C. IR (film): n=3106,
and
4-methylbenzene-1-sulfonyl
chloride
(423 mg,
2.22 mmol) were used. Flash column chromatography (hex-
anes/EtOAc=10:1) provided 1n as a yellow solid; yield:
444 mg (76%); mp 175–1778C. IR (film): n=3142, 2925,
1525, 1448, 1382, 1346, 1293 cmÀ1 1H NMR (300 MHz,
;
CDCl3): d=8.50 (d, J=1.9 Hz, 1H), 8.28 (dd, J=9.1, 2.1 Hz,
1H), 8.13 (d, J=9.2 Hz, 1H), 7.93 (d, J=7.8 Hz, 2H), 7.73
(s, 1H), 7.64 (t, J=7.5 Hz, 1H), 7.52 (t, J=7.6 Hz, 2H);
13C NMR (75 MHz, CDCl3): d=144.7, 137.3, 136.8, 135.0,
129.9, 128.6, 127.1, 125.3, 121.1, 116.0, 114.5, 114.3; HR-MS
(EI): m/z=335.9969, calcd. for C14H9ClN2O4S [M]+:
335.9966.
1
2855, 1491, 1477, 1383, 1359, 1296 cmÀ1; H NMR (300 MHz,
CDCl3): d=8.57 (s, 1H), 8.28–8.21 (m, 1H), 8.04–7.97 (m,
1H), 7.88 (d, J=8.1 Hz, 2H), 7.52–7.41 (m, 2H), 7.33 (d, J=
8.2 Hz, 2H), 2.40 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
146.9, 133.8, 133.6, 133.2, 130.6, 128.0, 127.6, 126.9, 126.0,
121.8, 121.3, 113.7, 21.8; HR-MS (ESI): m/z=317.0590,
calcd. for C15H13N2O4S [M+H]+: 317.0591.
3,6-Dichloro-1-(phenylsulfonyl)-1H-indole (1s): Following
the general procedure A, 3,6-dichloro-1H-indole (1.00 g,
5.38 mmol), THF (10.0 mL), 60% sodium hydride in oil
(194 mg, 4.85 mmol), and benzenesulfonyl chloride
(0.83 mL, 6.46 mmol) were used. Flash column chromatogra-
phy (hexanes/EtOAc=18:1) provided indole 1s as a white
solid; yield: 0.64 g (36%); mp 160–1638C. IR (film): n=
3-Chloro-5-methoxy-1-(phenylsulfonyl)-1H-indole
(1o):
Following the general procedure A, 3-chloro-5-methoxy-1H-
indole (970 mg, 5.34 mmol), THF (5.00 mL), DMF
(5.00 mL), 60% sodium hydride in oil (256 mg, 6.41 mmol),
and benzenesulfonyl chloride (0.68 mL, 5.34 mmol) were
used. Flash column chromatography (hexanes/EtOAc=9:1)
provided indole 1o as a white solid; yield: 1.15 g (67%); mp
142–1448C. IR (film): n=3131, 1479, 1446, 1372, 1216,
3142, 1605, 1581, 1448, 1420, 1372, 1306, 1269 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=8.04 (d, J=1.1 Hz, 1H),
7.92–7.86 (m, 2H), 7.63–7.53 (m, 2H), 7.52–7.43 (m, 3H),
7.31–7.26 (m, 1H); 13C NMR (75 MHz, CDCl3): d=137.6,
134.6, 134.4, 132.2, 129.7, 127.1, 127.0, 124.8, 122.9, 120.1,
114.0, 113.9; HR-MS (EI): m/z=324.9732, calcd. for
C14H9Cl2NO2S [M]+: 324.9726.
1169 cmÀ1 1H NMR (300 MHz, CDCl3): d=7.90 (d, J=
;
9.0 Hz, 1H), 7.85 (d, J=7.5 Hz, 2H), 7.59–7.49 (m, 2H),
7.44 (t, J=7.5 Hz, 2H), 7.04–6.89 (m, 2H), 3.83 (s, 3H);
13C NMR (75 MHz, CDCl3): d=157.1, 137.7, 134.2, 129.5,
129.5, 128.7, 126.9, 123.0, 115.6, 115.0, 114.1, 100.8, 55.8;
HR-MS (ESI): m/z=322.0302, calcd. for C15H13ClNO3S
[M+H]+: 322.0299.
3-Chloro-1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine
(1t): Following the general procedure A, 3-chloro-1H-pyrro-
lo[2,3-b]pyridine (1.00 g, 6.55 mmol), THF (10 mL), 60%
sodium hydride in oil (393 mg, 9.83 mmol), and benzenesul-
fonyl chloride (1.00 mL, 7.86 mmol) were used. Flash
column chromatography (hexanes/EtOAc=8:1) provided
indole 1t as a white solid; yield: 1.76 g (92%); mp 146–
1488C. IR (film): n=3148, 3060, 2360, 2341, 1395, 1381,
7-(Benzyloxy)-3-chloro-1-(phenylsulfonyl)-1H-indole (1p):
Following the general procedure A, 7-(benzyloxy)-3-chloro-
1H-indole (1.15 g, 4.45 mmol), THF (5.00 mL), DMF
(5.00 mL), 60% sodium hydride in oil (214 mg, 5.34 mmol),
and benzenesulfonyl chloride (0.57 mL, 4.45 mmol) were
used. Flash column chromatography (hexanes/EtOAc=
17:1) provided indole 1p as a light yellow solid; yield: 1.35 g
(76%); mp 134–1368C. IR (film): n=3151, 3062, 2937, 2877,
1
1284, 1200 cmÀ1; H NMR (300 MHz, CDCl3): d=8.49 (dd,
J=4.7, 1.3 Hz, 1H), 8.23–8.16 (m, 2H), 7.88 (dd, J=7.9, 1.5,
1H), 7.73 (s, 1H), 7.63–7.56 (m, 1H), 7.54–7.47 (m, 2H),
7.30–7.24 (m, 1H); 13C NMR (75 MHz, CDCl3): d=146.2,
145.8, 138.0, 134.4, 129.2, 128.1, 127.8, 122.6, 121.1, 119.5,
1
1368, 1341, 1228 cmÀ1; H NMR (300 MHz, CDCl3): d=7.86
(s, 1H), 7.58 (d, J=7.4 Hz, 2H), 7.47 (t, J=7.5 Hz, 1H),
7.40–7.35 (m, 3H), 7.33–7.27 (m, 4H), 7.21–7.12 (m, 2H),
6.74 (d, J=7.4 Hz, 1H), 5.01 (s, 2H); 13C NMR (75 MHz,
110.3; HR-MS (ESI): m/z=293.0147, calcd.
for
C13H10ClN2O2S [M+H]+: 293.0146.
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2-Allyl-1-tosyl-1H-indole (2b):[7b] Purification by flash
column chromatography (hexanes/EtOAc=10:1) provided
allylated indole 2b as a yellow oil; yield: 14 mg (11%).
1H NMR (300 MHz, CDCl3): d=8.16 (d, J=8.2 Hz, 1H),
7.65 (d, J=8.2 Hz, 2H), 7.41 (d, J=6.9 Hz, 1H), 7.24–7.16
(m, 4H), 6.39 (s, 1H), 6.12–5.97 (m, 1H), 5.25–5.15 (m, 2H),
3.77 (d, J=6.6 Hz, 2H), 2.34 (s, 3H).
(m, 1H), 6.06–5.89 (m, 1H), 5.11 (dd, J=10.2, 1.4 Hz, 1H),
4.98 (dd, J=17.2, 1.4 Hz, 1H), 4.07 (d, J=5.7 Hz, 2H), 3.93
(s, 3H), 3.71 (s, 3H); 13C NMR (75 MHz, CDCl3): d=166.4,
146.0, 136.8, 133.9, 126.5, 122.4, 121.9, 121.8, 116.6, 109.4,
104.1, 50.9, 29.9, 29.8; HR-MS (ESI): m/z=230.1179, calcd.
for C14H16NO2 [M+H]+: 230.1176.
Methyl 2-allyl-1-tosyl-1H-indole-3-carboxylate (2i): Purifi-
cation by flash column chromatography (hexanes/EtOAc=
8:1) provided allylated indole 2i as a yellow solid; yield:
109 mg (74%); mp 79–818C. IR (film): n=2951, 1712, 1451,
2-Allyl-N,N-dimethyl-1H-indole-1-carboxamide (2c):[33b]
Purification by flash column chromatography (hexanes/
EtOAc=6:1) provided allylated indole 2c as a yellow oil;
yield: 16 mg (18%). 1H NMR (300 MHz, CDCl3): d=7.53
(d, J=7.5 Hz, 1H), 7.25–7.00 (m, 3H), 6.38 (s, 1H), 6.08–
5.80 (m, 1H), 5.26–4.99 (m, 2H), 3.63 (d, J=6.3 Hz, 2H),
3.01 (br s, 6H).
1382, 1233, 1175, 1090 cmÀ1 1H NMR (300 MHz, CDCl3):
;
d=8.28–8.13 (m, 1H), 8.13–8.00 (m, 1H), 7.70 (d, J=8.4 Hz,
2H), 7.38–7.28 (m, 2H), 7.21 (d, J=8.1 Hz, 2H), 6.03 (ddt,
J=17.2, 10.1, 6.0 Hz, 1H), 5.19–5.03 (m, 2H), 4.33 (d, J=
6.0 Hz, 2H), 3.93 (s, 3H), 2.35 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=165.0, 146.7, 145.5, 135.9, 135.8, 134.7, 130.0,
127.3, 126.7, 125.0, 124.4, 121.9, 116.9, 114.6, 112.0, 51.5,
30.6, 21.6; HR-MS (ESI): m/z=370.1102, calcd. for
C20H20NO4S [M+H]+: 370.1108.
2-Allyl-3-methyl-1-tosyl-1H-indole (2d):[35] Purification by
flash column chromatography (hexanes/EtOAc=19:1) pro-
vided allylated indole 2d as a yellow solid; yield: 44 mg
1
(34%). H NMR (300 MHz, CDCl3): d=8.27–8.06 (m, 1H),
7.61 (d, J=8.3 Hz, 2H), 7.43–7.36 (m, 1H), 7.33–7.27 (m,
1H), 7.25–7.19 (m, 1H), 7.15 (d, J=8.1 Hz, 2H), 5.98 (ddt,
J=17.0, 10.2, 5.8 Hz, 1H), 5.08–4.94 (m, 2H), 3.79 (d, J=
5.8 Hz, 2H), 2.32 (s, 3H), 2.14 (s, 3H).
Methyl 2-allyl-1-(phenylsulfonyl)-1H-indole-3-carboxylate
(2j): Purification by flash column chromatography (hexanes/
EtOAc=8:1) provided allylated indole 2j as a yellow solid;
yield: 108 mg (76%); mp 92–948C. IR (film): n=3081, 3007,
2-Allyl-3-chloro-1-tosyl-1H-indole (2e): Purification by
flash column chromatography (hexanes/EtOAc=18:1) pro-
vided allylated indole 2e as a white solid; yield: 140 mg
(quantitative); mp 76–788C. IR (film): n=3078, 2923, 2854,
2951, 1713, 1449, 1383, 1233 cmÀ1
;
1H NMR (300 MHz,
CDCl3): d=8.27–8.17 (m, 1H), 8.14–8.04 (m, 1H), 7.82 (d,
J=7.3 Hz, 2H), 7.56 (t, J=7.5 Hz, 1H), 7.43 (t, J=7.7 Hz,
2H), 7.38–7.28 (m, 2H), 6.02 (ddt, J=17.2, 10.1, 6.0 Hz,
1H), 5.21–5.00 (m, 2H), 4.33 (d, J=6.0 Hz, 2H), 3.93 (s,
3H); 13C NMR (75 MHz, CDCl3): d=164.9, 146.6, 138.7,
135.9, 134.5, 134.3, 129.4, 127.2, 126.6, 125.1, 124.5, 122.0,
116.9, 114.6, 112.2, 51.6, 30.6; HR-MS (ESI): m/z=356.0946,
calcd. for C19H18NO4S [M+H]+: 356.0951.
1597, 1449, 1372, 1258, 1218 cmÀ1
;
1H NMR (300 MHz,
CDCl3): d=8.18 (d, J=7.8 Hz, 1H), 7.64 (d, J=8.2 Hz, 2H),
7.49 (d, J=7.6 Hz, 1H), 7.39–7.28 (m, 2H), 7.18 (d, J=
8.1 Hz, 2H), 6.08–5.92 (m, 1H), 5.17–5.03 (m, 2H), 3.88 (d,
J=5.8 Hz, 2H), 2.34 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=145.2, 135.5, 135.4, 134.2, 133.7, 129.9, 127.8, 126.6, 125.5,
124.2, 118.3, 117.0, 115.1, 114.4, 30.1, 21.6; HR-MS (ESI):
m/z=346.0676, calcd. for C18H17ClNO2S [M+H]+: 346.0663.
2-Allyl-3-chloro-1-(phenylsulfonyl)-1H-indole (2f): Purifi-
cation by flash column chromatography (hexanes/EtOAc=
15:1) provided allylated indole 2f as a yellow oil; yield:
129 mg (97%). IR (film): n=3069, 1449, 1429, 1375, 1310,
Methyl
2-allyl-1-(N,N-dimethylsulfamoyl)-1H-indole-3-
carboxylate (2k): Purification by flash column chromatogra-
phy (hexanes/EtOAc=7:1) provided allylated indole 2k as
a yellow solid; yield: 85 mg (66%); mp 62–658C. IR (film):
1
n=3082, 3055, 2951, 2852, 1699, 1556, 1451 cmÀ1; H NMR
(300 MHz, CDCl3): d=8.22–8.09 (m, 1H), 8.09–8.00 (m,
1H), 7.41–7.28 (m, 2H), 6.11–5.90 (m, 1H), 5.18–4.99 (m,
2H), 4.30 (d, J=5.8 Hz, 2H), 3.97 (s, 3H), 2.84 (s, 6H);
13C NMR (75 MHz, CDCl3): d=165.2, 147.0, 136.3, 134.7,
126.7, 124.7, 124.1, 121.8, 116.4, 114.6, 110.7, 51.5, 38.3, 30.6;
HR-MS (ESI): m/z=323.1062, calcd. for C15H19N2O4S [M+
H]+: 323.1060.
1
1295, 1258, 1221 cmÀ1; H NMR (300 MHz, CDCl3): d=8.21
(d, J=8.4 Hz, 1H), 7.77 (d, J=7.3 Hz, 2H), 7.57–7.46 (m,
2H), 7.44–7.28 (m, 4H), 6.11–5.90 (m, 1H), 5.20–5.02 (m,
2H), 3.90 (d, J=6.0 Hz, 2H); 13C NMR (75 MHz, CDCl3):
d=138.5, 135.4, 134.2, 134.1, 133.6, 129.3, 127.8, 126.5, 125.6,
124.3, 118.4, 117.1, 115.1, 114.6, 30.1; HR-MS (EI): m/z=
331.0434, calcd. for C17H14ClNO2S [M]+: 331.0428.
Methyl
2-allyl-1-[(4-nitrophenyl)sulfonyl]-1H-indole-3-
2-Allyl-3-chloro-N,N-dimethyl-1H-indole-1-sulfonamide
(2g): Purification by flash column chromatography (hex-
anes/EtOAc=18:1) provided allylated indole 2g as a yellow
oil; yield: 126 mg (quantitative). IR (film): n=3079, 2924,
carboxylate (2l): Purification by flash column chromatogra-
phy (hexanes/EtOAc=7:1) provided allylated indole 2l as
a yellow solid; yield: 101 mg (63%); mp 131–1348C. IR
(film): n=3106, 2952, 2924, 2853, 1713, 1534, 1387 cmÀ1
;
2854, 1449, 1414, 1372, 1261, 1223 cmÀ1; H NMR (300 MHz,
1H NMR (300 MHz, CDCl3): d=8.26 (d, J=9.0 Hz, 2H),
8.20–8.12 (m, 1H), 8.12–8.05 (m, 1H), 7.98 (d, J=9.0 Hz,
2H), 7.42–7.30 (m, 2H), 6.01 (ddt, J=17.1, 10.2, 6.0 Hz,
1H), 5.12 (dd, J=17.1, 1.5 Hz, 1H), 5.08 (dd, J=10.1,
1.43 Hz, 1H), 4.33 (d, J=6.0 Hz, 2H), 3.95 (s, 3H);
13C NMR (75 MHz, CDCl3): d=164.6, 150.7, 146.3, 143.8,
135.7, 134.3, 128.1, 127.4, 125.7, 125.2, 124.7, 122.4, 117.4,
114.4, 113.4, 51.8, 30.5; HR-MS (ESI): m/z=399.0668, calcd.
for C19H15N2O6S [MÀH]À: 399.0656.
1
CDCl3): d=8.10–8.00 (m, 1H), 7.62–7.53 (m, 1H), 7.39–7.28
(m, 2H), 6.07–5.91 (m, 1H), 5.17–5.06 (m, 2H), 3.87 (d, J=
5.8 Hz, 2H), 2.79 (s, 6H); 13C NMR (75 MHz, CDCl3): d=
135.7, 134.4, 133.7, 127.0, 125.0, 123.6, 118.2, 116.7, 115.0,
112.6, 38.4, 30.0; HR-MS (EI): m/z=298.0542, calcd. for
C13H15ClN2O2S [M]+: 298.0537.
Methyl 2-allyl-1-methyl-1H-indole-3-carboxylate (2h): Pu-
rification by flash column chromatography (hexanes/
EtOAc=8:1) provided allylated indole 2h as a yellow solid;
yield: 65 mg (71%); mp 81–828C. IR (film): n=3075, 2996,
Methyl 2-allyl-1-(dimethylcarbamoyl)-1H-indole-3-carbox-
ylate (2m): Purification by flash column chromatography
(hexanes/EtOAc=6:1) provided allylated indole 2m as
a yellow solid; yield: 70 mg (61%); mp 84–858C. IR (film):
2947, 2841, 1694, 1533, 1213 cmÀ1
;
1H NMR (300 MHz,
CDCl3): d=8.19–8.10 (m, 1H), 7.37–7.27 (m, 2H), 7.25–7.20
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n=3079, 2949, 2854, 1697, 1456, 1386, 1271 cmÀ1; H NMR
(300 MHz, CDCl3): d=8.23–8.05 (m, 1H), 7.37–7.13 (m,
3H), 6.04–5.78 (m, 1H), 5.21–5.02 (m, 2H), 4.33 (d, J=
12.9 Hz, 1H), 3.95 (s, 3H), 3.93–3.83 (m, 1H), 3.21 (s, 3H),
2.72 (s, 3H); 13C NMR (75 MHz, CDCl3): d=165.7, 152.6,
145.0, 134.4, 133.9, 126.2, 123.7, 122.7, 122.1, 116.9, 110.4,
106.7, 51.1, 38.4, 36.8, 30.1; HR-MS (ESI): m/z=287.1391,
calcd. for C16H19N2O3 [M+H]+: 287.1390.
2925, 2853, 1448, 1420, 1378, 1291, 1277 cmÀ1 1H NMR
;
1
(300 MHz, CDCl3): d=8.24 (d, J=1.0 Hz, 1H), 7.76 (d, J=
7.5 Hz, 2H), 7.57 (t, J=7.4 Hz, 1H), 7.49–7.39 (m, 3H),
7.33–7.26 (m, 1H), 6.05–5.85 (m, 1H), 5.13–5.04 (m, 2H),
3.84 (d, J=6.0 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=
138.2, 135.6, 134.7, 134.3, 133.1, 131.5, 129.5, 126.5, 126.2,
124.9, 119.1, 117.2, 115.2, 114.0, 30.0; HR-MS (EI): m/z=
365.0045, calcd. for C17H13Cl2NO2S [M]+: 365.0039.
2-Allyl-3-chloro-5-methoxy-1-(phenylsulfonyl)-1H-indole
(2o): Purification by flash column chromatography (hex-
anes/EtOAc=16:1) provided allylated indole 2o as a yellow
oil; yield: 124 mg (86%); IR (film): n=3080, 3005, 2937,
2-Allyl-3-chloro-1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyri-
dine (2t): Purification by flash column chromatography
(hexanes/EtOAc=9:1) provided allylated indole 2t as
a yellow solid; yield: 119 mg (89%); mp 93–958C. IR (film):
2835, 1615, 1479, 1448, 1372 cmÀ1
;
1H NMR (300 MHz,
n=3070, 2924, 1582, 1449, 1398, 1380, 1331, 1276 cmÀ1
;
CDCl3): d=8.08 (d, J=9.0 Hz, 1H), 7.72 (d, J=8.1 Hz, 2H),
7.52 (t, J=7.0 Hz, 1H), 7.39 (t, J=7.7 Hz, 2H), 7.00–6.87
(m, 2H), 6.09–5.87 (m, 1H), 5.17–5.04 (m, 2H), 3.90–3.81
(m, 2H), 3.84 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
157.2, 138.4, 134.8, 134.0, 133.6, 129.9, 129.3, 128.9, 126.5,
117.1, 116.3, 114.7, 114.6, 100.4, 55.8, 30.2; HR-MS (EI): m/
z=361.0536, calcd. for C18H16ClNO3S [M]+: 361.0534.
1H NMR (300 MHz, CDCl3): d=8.43 (dd, J=4.8, 3.2 Hz,
1H), 8.22–8.13 (m, 2H), 7.78 (dd, J=7.8, 1.6 Hz, 1H), 7.59–
7.51 (m, 1H), 7.49–7.41 (m, 2H), 7.25–7.18 (m, 1H), 6.17–
6.02 (m, 1H), 5.20–5.09 (m, 2H), 4.05–3.99 (m, 2H);
13C NMR (75 MHz, CDCl3): d=146.9, 145.2, 138.7, 135.3,
134.2, 133.7, 128.9, 128.2, 126.6, 120.0, 119.5, 117.3, 110.5,
29.8;
HR-MS
(ESI):
m/z=333.0460,
calcd.
for
2-Allyl-7-(benzyloxy)-3-chloro-1-(phenylsulfonyl)-1H-
C16H14ClN2O2S [M+H]+: 333.0459.
indole (2p): Purification by flash column chromatography
(hexanes/EtOAc=18:1) provided allylated indole 2p as
a yellow solid; yield: 141 mg (80%); mp 98–998C. IR (film):
1-Allyl-3-nitro-1H-indole (3): Purification by flash column
chromatography (hexanes/EtOAc=7:1) provided N-allylat-
ed indole 3 as a yellow solid; yield: 53 mg (52%); mp 82–
858C. IR (film): n=3132, 1484, 1458, 1445, 1371, 1351, 1307,
1
n=3085, 3068, 3035, 2940, 1494, 1352, 1271 cmÀ1; H NMR
(300 MHz, CDCl3): d=7.66 (d, J=7.4 Hz, 2H), 7.45 (t, J=
7.4 Hz, 1H), 7.38–7.27 (m, 5H), 7.25–7.18 (m, 2H), 7.18–
7.11 (m, 2H), 6.76–6.65 (m, 1H), 6.16–5.94 (m, 1H), 5.25–
5.10 (m, 2H), 4.92 (s, 2H), 4.02 (d, J=6.1 Hz, 2H);
13C NMR (75 MHz, CDCl3): d=146.7, 141.2, 137.3, 136.3,
134.3, 132.7, 130.5, 128.6, 128.5, 127.9, 127.5, 126.2, 125.5,
125.1, 117.2, 114.2, 111.1, 109.8, 70.7, 31.0; HR-MS (ESI): m/
z=438.0927, calcd. for C24H21ClNO3S [M+H]+: 438.0925.
2-Allyl-3-chloro-1-(phenylsulfonyl)-1H-indole-4-carboni-
trile (2q): Purification by flash column chromatography
(hexanes/EtOAc=9:1) provided allylated indole 2q as
a yellow oil; yield: 127 mg (89%); IR (film): n=3082, 2227,
1210 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.33–8.25 (m,
;
1H), 8.11 (s, 1H), 7.44–7.33 (m, 3H), 6.09–5.94 (m, 1H),
5.37 (d, J=10.2 Hz, 1H), 5.24 (d, J=17.1 Hz, 1H), 4.79 (d,
J=5.6 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=135.3,
131.1, 130.5, 124.7, 124.4, 121.1, 121.0, 120.0, 110.9, 110.1,
49.9; HR-MS (ESI): m/z=203.0815, calcd. for C11H11N2O2
[M+H]+: 203.0815.
3-Chloro-2-cinnamyl-1-tosyl-1H-indole (4a): Purification
by flash column chromatography (hexanes/EtOAc=12:1)
provided allylated indole 4a as a yellow solid; yield: 160 mg
(95%); mp 104–1078C. IR (film): n=3056, 3028, 2924, 1449,
1
1372, 1178, 1094 cmÀ1; H NMR (300 MHz, CDCl3): d=8.22
1
1448, 1423, 1380, 1359, 1262, 1240 cmÀ1; H NMR (300 MHz,
(d, J=7.7 Hz, 1H), 7.64 (d, J=8.3 Hz, 2H), 7.55–7.47 (m,
1H), 7.46–7.27 (m, 5H), 7.24–7.15 (m, 2H), 7.09 (d, J=
8.3 Hz, 2H), 6.41 (d, J=16.0 Hz, 1H), 6.28 (dt, J=15.9,
6.1 Hz, 1H), 4.04 (d, J=6.0 Hz, 2H), 2.26 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=145.2, 137.1, 135.6, 135.5, 134.3, 132.1,
129.9, 128.5, 127.7, 127.3, 126.6, 126.3, 125.6, 125.3, 124.2,
118.4, 115.1, 114.3, 29.2, 21.6; HR-MS (ESI): m/z=439.1246,
calcd. for C24H24ClN2O2S [M+NH4]+: 439.1242.
CDCl3): d=8.45 (d, J=8.6 Hz, 1H), 7.76 (d, J=8.1 Hz, 2H),
7.66–7.55 (m, 2H), 7.50–7.37 (m, 3H), 6.04–5.84 (m, 1H),
5.18–5.05 (m, 2H), 3.92 (d, J=6.0 Hz, 2H); 13C NMR
(75 MHz, CDCl3): d=138.0, 137.8, 135.6, 134.7, 132.6, 130.5,
129.7, 127.2, 126.6, 125.1, 119.4, 117.8, 116.7, 112.8, 102.6,
30.0; HR-MS (EI): m/z=356.0388, calcd. for C18H13ClN2O2S
[M]+: 356.0381.
2-Allyl-3-chloro-5-nitro-1-(phenylsulfonyl)-1H-indole (2r):
Purification by flash column chromatography (hexanes/
EtOAc=10:1) provided allylated indole 2r as a yellow
solid; yield: 116 mg (77%); mp 121–1248C. IR (film): n=
3-Chloro-2-[3-(4-chlorophenyl)allyl]-1-tosyl-1H-indole
(4b): Purification by flash column chromatography (hex-
anes/EtOAc=18:1) provided allylated indole 4b as a yellow
solid; yield: 119 mg (65%); mp 98–1018C. IR (film): n=
1
3087, 1524, 1447, 1382, 1345, 1268 cmÀ1; H NMR (300 MHz,
3053, 2980, 2924, 1491, 1449, 1371, 1249 cmÀ1 1H NMR
;
CDCl3): d=8.43 (d, J=2.2 Hz, 1H), 8.33 (d, J=9.2 Hz, 1H),
8.24 (dd, J=9.3, 2.2 Hz, 1H), 7.79 (d, J=7.5 Hz, 2H), 7.61
(t, J=7.5 Hz, 1H), 7.48 (t, J=7.6 Hz, 2H), 6.03–5.87 (m,
1H), 5.15–5.01 (m, 2H), 3.90 (d, J=6.0 Hz, 2H); 13C NMR
(75 MHz, CDCl3): d=144.7, 138.1, 138.0, 137.6, 134.8, 132.6,
129.8, 127.9, 126.7, 120.5, 117.8, 115.4, 114.8, 114.4, 30.1;
HR-MS (ESI): m/z=394.0638, calcd. for C17H17ClN3O4S
[M+NH4]+: 394.0623.
2-Allyl-3,6-dichloro-1-(phenylsulfonyl)-1H-indole (2s): Pu-
rification by flash column chromatography (hexanes/
EtOAc=19:1) provided allylated indole 2s as a white solid;
yield: 130 mg (89%); mp 98–1018C. IR (film): n=3078,
(300 MHz, CDCl3): d=8.21 (d, J=7.5 Hz, 1H), 7.62 (d, J=
8.4 Hz, 2H), 7.55–7.47 (m, 1H), 7.40–7.29 (m, 2H), 7.25–
7.17 (m, 4H), 7.10 (d, J=8.0 Hz, 2H), 6.37 (d, J=16.1 Hz,
1H), 6.27 (dt, J=15.9, 5.5 Hz, 1H), 4.02 (d, J=5.4 Hz, 2H),
2.28 (s, 3H); 13C NMR (75 MHz, CDCl3): d=145.2, 135.62,
135.59, 135.5, 134.0, 132.9, 130.9, 129.9, 128.6, 127.7, 127.5,
126.6, 126.1, 125.7, 124.2, 118.4, 115.1, 114.4, 29.2, 21.6; HR-
MS (ESI): m/z=473.0856, calcd. for C24H23Cl2N2O2S [M+
NH4]+: 473.0852.
3-Chloro-2-[3-(2-methoxyphenyl)allyl]-1-tosyl-1H-indole
(4c): Purification by flash column chromatography (hexanes/
EtOAc=8:1) provided allylated indole 4c as a yellow solid;
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9
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yield: 167 mg (92%); mp 74–768C. IR (film): n=3051, 2936,
2836, 1597, 1488, 1454, 1373 cmÀ1 1H NMR (300 MHz,
(m, 5H), 2.14–2.07 (m, 1H), 1.68–1.61 (m, 1H), 1.49–1.41
(m, 2H), 1.10 (d, J=10.3 Hz, 1H), 0.92 (d, J=10.2 Hz, 1H);
13C NMR (75 MHz, CDCl3): d=146.0, 144.7, 136.9, 135.9,
134.7, 129.9, 129.8, 126.4, 124.1, 123.5, 121.8, 118.6, 114.9,
111.6, 49.4, 44.3, 43.7, 42.2, 35.0, 31.9, 31.5, 28.2, 21.7; HR-
MS (ESI): m/z=404.1689, calcd. for C25H26NO2S [M+H]+:
404.1679.
;
CDCl3): d=8.29–8.14 (m, 1H), 7.65 (d, J=8.4 Hz, 2H),
7.55–7.47 (m, 1H), 7.40–7.28 (m, 3H), 7.22–7.08 (m, 3H),
6.92–6.79 (m, 3H), 6.29 (dt, J=16.0, 6.6 Hz, 1H), 4.06 (d,
J=6.6 Hz, 2H), 3.82 (s, 3H), 2.27 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=156.5, 145.1, 135.6, 135.4, 134.6, 129.8,
128.4, 127.8, 127.1, 126.8, 126.6, 126.1, 125.9, 125.4, 124.1,
120.6, 118.3, 115.1, 114.1, 110.8, 55.5, 29.8, 21.5; HR-MS
(ESI): m/z=469.1367, calcd. for C25H26ClN2O3S [M+NH4]+:
469.1347.
2-Methyl-9H-carbazole (6a):[36] The reaction was carried
out with 2-allyl-3-chloroindole 2e. Purification by flash
column chromatography (hexanes/EtOAc=19:1) provided
1
carbazole 6a as a yellow solid; yield: 28 mg (77%). H NMR
3-Chloro-2-[3-(3-methoxyphenyl)allyl]-1-tosyl-1H-indole
(4d): Purification by flash column chromatography (hex-
anes/EtOAc=8:1) provided allylated indole 4d as a yellow
solid; yield: 125 mg (69%); mp 127–1298C. IR (film): n=
(300 MHz, CDCl3): d=8.03 (d, J=7.4 Hz, 1H), 7.99–7.86
(m, 2H), 7.45–7.32 (m, 2H), 7.24–7.17 (m, 2H), 7.06 (d, J=
7.6 Hz, 1H), 2.53 (s, 3H).
6-Methoxy-2-methyl-9H-carbazole (6b):[37] The reaction
was carried out with 2-allyl-3-chloroindole 2o. Purification
by flash column chromatography (hexanes/EtOAc=12:1)
provided carbazole 6b as a yellow solid; yield: 34 mg (80%).
1H NMR (300 MHz, CDCl3): d=7.92 (d, J=8.0 Hz, 1H),
7.77 (br s, 1H), 7.53 (d, J=2.0 Hz, 1H), 7.27 (d, J=8.7 Hz,
1H), 7.14 (s, 1H), 7.09–6.99 (m, 2H), 3.94 (s, 3H), 2.52 (s,
3H).
1
3031, 2933, 2834, 2359, 1372, 1308 cmÀ1; H NMR (300 MHz,
CDCl3): d=8.22 (d, J=8.3 Hz, 1H), 7.64 (d, J=8.1 Hz, 2H),
7.52 (d, J=7.3 Hz, 1H), 7.40–7.29 (m, 2H), 7.18 (t, J=
7.8 Hz, 1H), 7.10 (d, J=8.1 Hz, 2H), 6.87 (d, J=7.2 Hz,
1H), 6.81–6.71 (m, 2H), 6.39 (d, J=16.1 Hz, 1H), 6.33–6.21
(m, 1H), 4.03 (d, J=5.8 Hz, 2H), 3.79 (s, 3H), 2.27 (s, 3H);
13C NMR (75 MHz, CDCl3): d=159.8, 145.2, 138.6, 135.6,
135.5, 134.2, 132.1, 130.0, 129.5, 127.8, 126.7, 125.64, 125.59,
124.2, 119.0, 118.4, 115.2, 114.4, 113.2, 111.4, 55.3, 29.2, 21.6;
HR-MS (ESI): m/z=452.1086, calcd. for C25H23ClNO3S
[M+H]+: 452.1082.
1-(Benzyloxy)-7-methyl-9H-carbazole (6c): The reaction
was carried out with 2-allyl-3-chloroindole 2p. Purification
by flash column chromatography (hexanes/EtOAc=18:1)
provided carbazole 6c as a yellow solid; yield: 41 mg (71%);
mp 114–1158C. IR (film): n=3416, 3034, 2915, 2868, 1578,
3-Chloro-2-[3-(4-methoxyphenyl)allyl]-1-tosyl-1H-indole
(4e): Purification by flash column chromatography (hex-
anes/EtOAc=17:1) provided allylated indole 4e as a yellow
oil; yield: 126 mg (70%). IR (film): n=3033, 3003, 2956,
1
1452, 1261, 1242 cmÀ1; H NMR (300 MHz, CDCl3): d=8.20
(br s, 1H), 7.94 (d, J=7.9 Hz, 1H), 7.67 (d, J=7.8 Hz, 1H),
7.58–7.49 (m, 2H), 7.48–7.36 (m, 3H), 7.22 (s, 1H), 7.14 (t,
J=7.8 Hz, 1H), 7.07 (d, J=7.8 Hz, 1H), 6.96 (d, J=7.8 Hz,
1H), 5.26 (s, 2H), 2.53 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=144.9, 139.7, 137.1, 136.0, 129.9, 128.8, 128.3, 128.1, 124.7,
121.4, 121.1, 120.3, 119.7, 113.0, 111.1, 106.9, 70.5, 22.2; HR-
MS (ESI): m/z=288.1388, calcd. for C20H18NO [M+H]+:
288.1383.
1
2933, 2836, 1373 cmÀ1; H NMR (300 MHz, CDCl3): d=8.22
(d, J=7.7 Hz, 1H), 7.65 (d, J=8.1 Hz, 2H), 7.51 (d, J=
7.1 Hz, 1H), 7.39–7.29 (m, 2H), 7.21 (d, J=8.5 Hz, 2H),
7.09 (d, J=8.1 Hz, 2H), 6.81 (d, J=8.5 Hz, 2H), 6.38 (d, J=
15.9 Hz, 1H), 6.23–6.09 (m, 1H), 4.02 (d, J=6.1 Hz, 2H),
3.80 (s, 3H), 2.27 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
159.0, 145.1, 135.6, 135.4, 134.6, 131.5, 129.93, 129.89, 127.8,
127.4, 126.6, 125.5, 124.2, 123.1, 118.3, 115.1, 114.1, 113.9,
55.3, 29.2, 21.6; HR-MS (ESI): m/z=452.1100, calcd. for
C25H23ClNO3S [M+H]+: 452.1082.
7-Methyl-9H-carbazole-4-carbonitrile (6d): The reaction
was carried out with 2-allyl-3-chloroindole 2q. Purification
by flash column chromatography (hexanes/EtOAc=6:1)
provided carbazole 6d as a yellow solid; yield: 23 mg (56%);
mp 134–1368C. IR (film): n=3332, 2921, 2854, 2219, 1438,
3-Chloro-2-cinnamyl-1-(phenylsulfonyl)-1H-pyrrolo[2,3-
b]pyridine (4f): Purification by flash column chromatogra-
phy (hexanes/EtOAc=6:1) provided allylated indole 4f as
a yellow solid; yield: 136 mg (83%); mp 118–1208C. IR
1325 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.43 (d, J=
;
8.1 Hz, 1H), 8.25 (br s, 1H), 7.62 (d, J=8.1 Hz, 1H), 7.51
(d, J=7.2 Hz, 1H), 7.40 (t, J=7.8 Hz, 1H), 7.31–7.26 (m,
1H), 7.15 (d, J=8.1 Hz, 1H), 2.55 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=140.6, 139.3, 138.4, 124.9, 124.5, 123.9,
122.2, 121.5, 119.1, 118.9, 115.2, 111.1, 103.4, 22.3; HR-MS
(EI) : m/z=206.0845, calcd. for C14H10N2 [M]+: 206.0844.
7-Methyl-9H-pyrido[2,3-b]indole (6e):[38] The reaction was
carried out with 2-allyl-3-chloroindole 2t. Purification by
flash column chromatography (hexanes/EtOAc=1:1) pro-
vided carbazole 6e as a yellow solid; yield: 26 mg (71%).
1H NMR (300 MHz, DMSO-d6): d=11.68 (s, 1H), 8.51–8.30
(m, 2H), 8.01 (d, J=6.4 Hz, 1H), 7.30 (s, 1H), 7.22–7.11 (m,
1H), 7.04 (d, J=6.9 Hz, 1H), 2.47 (s, 3H).
(film): n=3059, 2360, 2341, 1398, 1380 cmÀ1
;
1H NMR
(300 MHz, CDCl3): d=8.47 (d, J=4.8 Hz, 1H), 8.18 (d, J=
7.8 Hz, 2H), 7.82 (d, J=7.8 Hz, 1H), 7.49 (t, J=7.4 Hz,
1H), 7.37–7.28 (m, 6H), 7.25–7.19 (m, 2H), 6.52–6.37 (m,
2H), 4.18 (d, J=4.6 Hz, 2H); 13C NMR (75 MHz, CDCl3):
d=147.0, 145.3, 138.8, 137.0, 135.6, 134.1, 132.5, 128.9, 128.6,
128.4, 127.6, 126.7, 126.4, 125.5, 120.1, 119.6, 110.5, 29.0;
HR-MS (ESI): m/z=409.0788, calcd. for C22H18ClN2O2S
[M+H]+: 409.0772.
5-Methylene-7-tosyl-2,3,4,4a,5,6,7,11c-octahydro-1H-1,4-
methanobenzo[c]carbazole (5): Purification by flash column
chromatography (hexanes/EtOAc=20:1) provided carba-
zole 5 as a yellow oil; yield: 76 mg (94%). IR (film): n=
2-Benzyl-9H-carbazole (6f): The reaction was carried out
with 2-allyl-3-chloroindole 4a. Purification by flash column
chromatography (hexanes/EtOAc=18:1) provided carba-
zole 6f as a yellow solid; yield: 32 mg (62%); mp 189–
1908C. IR (film): n=3398, 3022, 2921, 1462, 1443,
1
3068, 2953, 2871, 1452, 1369, 1217 cmÀ1; H NMR (300 MHz,
CDCl3): d=8.14 (d, J=6.8 Hz, 1H), 7.60 (d, J=7.0 Hz, 2H),
7.40 (d, J=6.9 Hz, 1H), 7.25–7.14 (m, 4H), 5.01–4.84 (m,
2H), 3.91 (d, J=18.6 Hz, 1H), 3.56 (d, J=18.4 Hz, 1H),
2.97 (d, J=7.8 Hz, 1H), 2.56 (d, J=8.2 Hz, 1H), 2.37–2.26
1343 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.04 (d, J=
;
7.7 Hz, 1H), 8.01–7.85 (m, 2H), 7.42–7.36 (m, 2H), 7.34–
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7.28 (m, 2H), 7.26–7.16 (m, 5H), 7.11 (d, J=7.9 Hz, 1H),
4.16 (s, 2H); 13C NMR (75 MHz, DMSO-d6): d=141.9,
140.2, 139.9, 139.1, 128.9, 128.5, 126.0, 125.3, 122.5, 120.7,
120.2, 120.0, 119.9, 118.6, 111.0, 110.9, 41.8; HR-MS (ESI):
m/z=258.1283, calcd. for C19H16N [M+H]+: 258.1277.
(q, J=7.5 Hz, 2H), 2.53 (s, 3H), 2.27 (s, 3H), 1.31 (t, J=
7.5 Hz, 3H), 1.19 (t, J=7.5 Hz, 3H); 13C NMR (75 MHz,
CDCl3): d=144.7, 138.5, 137.13, 137.07, 136.3, 136.2, 135.3,
129.7, 126.8, 126.6, 126.1, 123.8, 122.4, 122.3, 114.9, 114.2,
22.8, 21.8, 21.6, 21.4, 15.0, 14.3; HR-MS (ESI): m/z=
392.1688, calcd. for C24H26NO2S [M+H]+: 392.1679.
2-(2-Methoxybenzyl)-9H-carbazole (6g): The reaction was
carried out with 2-allyl-3-chloroindole 4c. Purification by
flash column chromatography (hexanes/EtOAc=10:1) pro-
vided carbazole 6g as a yellow solid; yield: 27 mg (47%);
mp 148–1498C. IR (film): n=3410, 2360, 1491, 1460, 1440,
2-Methyl-3,4-diphenyl-9-tosyl-9H-carbazole (7b): Follow-
ing the procedure to prepare 7a, Cs2CO3 (130 mg,
0.40 mmol), 2e (69.2 mg, 0.20 mmol), 1,2-diphenylethyne
(285 mg, 1.6 mmol), 1,4-dioxane (1.00 mL, 0.20M),
Pd(OAc)2 (4.50 mg, 0.020 mmol) and P(t-Bu)3HBF4
(12.8 mg, 0.044 mmol) were used. Purification by flash
column chromatography (hexanes/EtOAc=19:1) provided
carbazole 7b as a white solid; yield: 64 mg (66%); mp 254–
2568C. IR (film): n=3055, 1592, 1443, 1371, 1230,
1242 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.04 (d, J=
;
7.7 Hz, 1H), 7.98 (d, J=7.9 Hz, 1H), 7.85 (br s, 1H), 7.43–
7.33 (m, 2H), 7.26–7.18 (m, 3H), 7.17–7.10 (m, 2H), 6.96–
6.88 (m, 2H), 4.16 (s, 2H), 3.85 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=157.4, 140.0, 139.6, 139.3, 130.5, 130.1, 127.5,
125.4, 123.4, 121.5, 121.0, 120.6, 120.2, 120.1, 119.4, 110.9,
110.6, 110.5, 55.5, 36.3; HR-MS (ESI): m/z=288.1378, calcd.
for C20H18NO [M+H]+: 288.1383.
1175 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.35–8.25 (m,
;
2H), 7.82 (d, J=8.3 Hz, 2H), 7.33 (t, J=7.8 Hz, 1H), 7.23–
7.05 (m, 10H), 7.01 (d, J=6.5 Hz, 2H), 6.95 (t, J=7.6 Hz,
1H), 6.45 (d, J=7.9 Hz, 1H), 2.34 (s, 3H), 2.30 (s, 3H);
13C NMR (75 MHz, CDCl3): d=145.0, 139.7, 139.1, 138.6,
137.8, 137.6, 136.14, 136.12, 135.4, 130.4, 129.9, 128.2, 127.7,
127.1, 126.8, 126.60, 126.56, 126.3, 123.4, 122.4, 122.0, 114.8,
114.6, 22.5, 21.7; HR-MS (ESI): m/z=488.1671, calcd. for
C32H26NO2S [M+H]+: 488.1679.
2-(3-Methoxybenzyl)-9H-carbazole (6h): The reaction was
carried out with 2-allyl-3-chloroindole 4d. Purification by
flash column chromatography (hexanes/EtOAc=16:1) pro-
vided carbazole 6h as a yellow solid; yield: 30 mg (52%);
mp 172–1748C. IR (film): n=3405, 2936, 2360, 1595, 1461,
1441 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.05 (d, J=
;
7.7 Hz, 1H), 7.99 (d, J=7.9 Hz, 1H), 7.86 (br s, 1H), 7.44–
7.34 (m, 2H), 7.29–7.21 (m, 2H), 7.17 (s, 1H), 7.12 (d, J=
8.0 Hz, 1H), 6.91–6.75 (m, 3H), 4.13 (s, 2H), 3.79 (s, 3H);
13C NMR (75 MHz, CDCl3): d=159.8, 143.2, 140.0, 139.7,
139.2, 129.6, 125.6, 123.4, 121.7, 121.6, 121.0, 120.3, 120.2,
119.5, 114.9, 111.4, 110.9, 110.6, 55.3, 42.5; HR-MS (ESI):
m/z=288.1386, calcd. for C20H18NO [M+H]+: 288.1383.
2-(4-Methoxybenzyl)-9H-carbazole (6i): The reaction was
carried out with 2-allyl-3-chloroindole 4e. Purification by
flash column chromatography (hexanes/EtOAc=7:1) pro-
vided carbazole 6i as a yellow solid; yield: 30 mg (52%); mp
199–2008C. IR (film): n=3397, 2360, 1609, 1511, 1461,
Acknowledgements
This work was supported by a 2-Year Research Grant of
Pusan National University. We thank Prof. Jin Kyoon Park
for helpful discussions.
References
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7.17 (m, 3H), 7.15 (s, 1H), 7.09 (d, J=8.0 Hz, 1H), 6.84 (d,
J=8.6 Hz, 2H), 4.10 (s, 2H), 3.79 (s, 3H); 13C NMR
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3,4-Diethyl-2-methyl-9-tosyl-9H-carbazole (7a): To an 8-
mL glass vial equipped with a magnetic stir bar were se-
quentially added Cs2CO3 (130 mg, 0.40 mmol), 2e (69.2 mg,
0.20 mmol), hex-3-yne (182 mL, 1.6 mmol), 1,4-dioxane
(1.00 mL, 0.20M), Pd(OAc)2 (4.50 mg, 0.020 mmol) and P(t-
Bu)3HBF4 (12.8 mg, 0.044 mmol). The reaction mixture was
purged with nitrogen through a Teflon-lined cap. Then, the
cap was replaced with a new Teflon-lined solid cap. The re-
action vial was moved to a preheated reaction block
(1308C). After stirring for 20 h, the reaction mixture was
cooled to 258C and concentrated. The residue was purified
by flash column chromatography (hexanes/EtOAc=19:1) to
provide carbazole 7a as a white solid; yield: 69 mg (88%);
mp 179–1828C. IR (film): n=2968, 2931, 2872, 1442, 1368,
1174 cmÀ1 1H NMR (300 MHz, CDCl3): d=8.36 (d, J=
;
8.2 Hz, 1H), 8.06 (s, 1H), 7.98 (d, J=7.7 Hz, 1H), 7.71 (d,
J=8.2 Hz, 2H), 7.43 (t, J=7.8 Hz, 1H), 7.34 (t, J=7.2 Hz,
1H), 7.11 (d, J=8.1 Hz, 2H), 3.15 (q, J=7.5 Hz, 2H), 2.78
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These are not the final page numbers!

UPDATES
14 Catalytic C-2 Allylation of Indoles by Electronic
Modulation of the Indole Ring and its Application to the
Synthesis of Functionalized Carbazoles
Adv. Synth. Catal. 2016, 358, 1 – 14
Ju Young Lee, Hyeri Ha, Seri Bae, Inhyuk Han,
Jung Min Joo*
Adv. Synth. Catal. 0000, 000, 0 – 0
14
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!