Direct palladium-catalyzed C-3 alkynylation of indoles

Article abstract of DOI:10.1016/j.tetlet.2008.11.097

The direct palladium-catalyzed coupling reaction of indoles with alkynyl bromides was described in this paper. In the presence of catalytic amount of PdCl₂(PPh₃)₂ and 2.0 equiv. NaOAc, the coupling reaction of indoles with

Full text of DOI:10.1016/j.tetlet.2008.11.097

Tetrahedron Letters 50 (2009) 763–766
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Tetrahedron Letters
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Direct palladium-catalyzed C-3 alkynylation of indoles
*
Yonghong Gu , Xue-min Wang
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 23 July 2008
Revised 24 November 2008
Accepted 26 November 2008
Available online 30 November 2008
The direct palladium-catalyzed coupling reaction of indoles with alkynyl bromides was described in this
paper. In the presence of catalytic amount of PdCl2(PPh3)2 and 2.0 equiv. NaOAc, the coupling reaction of
indoles with alkynyl bromides proceeded smoothly at 50 °C to give the corresponding 3-alkynylindoles
with high regioselectivity in good to excellent yields.
Ó 2008 Elsevier Ltd. All rights reserved.
Indole derivatives are one of the most privileged structural mo-
tifs frequently found in natural products and pharmaceuticals.1
Many efficient methods for the synthesis and functionalization of
indoles have been developed in recent years;2 among them the di-
rect functionalization of heterocyclic C–H bonds is one of the most
attractive processes. During last two decades, the significant pro-
gress in the development of transition metal-catalyzed direct ary-
lation3 and vinylation4 of indoles has been achieved. This approach
provides direct coupling of indoles with arene derivatives and al-
kenes. However, direct C–H alkynylation of indoles has not been
reported yet. Until recently, Gevorgyan and co-workers developed
direct palladium-catalyzed alkynylation reaction of electron-rich
heterocycles with alkylnyl halides.5 This work encouraged us to
examine the possibility of preparing 3-alkynylindoles by a similar
strategy.
conditions, Pd(OAc)2 and PdCl2 completely failed to yield any
coupled products (entries 4 and 5). However, when PdCl2(PPh3)2
and Pd(PPh3)4 were applied as the catalysts, the coupling reac-
tion of indole and bromoalkyne led to 3-alkynylindole in 89%
and 85% yields respectively (entries 3 and 6). Notably, in the
absence of Pd catalyst, using Cu(OAc)2 or CuI as a catalyst, the
reaction could not occur (entries 1 and 2).
Next, an examination of selected bases revealed that NaOAc and
KOAc were effective to this transformation (entries 6 and 7).
However, the use of stronger bases such as Cs2CO3, K2CO3, and
t-BuOK did not give the coupled product 3a (entries 9–11). It
Table 1
Reaction optimization for C-3 alkynylation of indolea
Typically, 3-alkynylindoles were prepared from the Sonogashira
reaction of 3-functionalized indoles with alkynes.6 While these
reactions are often synthetically useful, they usually require
protection of heteorocyclic nitrogen atom of indoles and prefunc-
tionalization of indoles. The other method included preparation
of 2-substituted 3-alkynylinoles via palladium-catalyzed reaction
of 1-bromoalkynes with o-alkynyltrifluoroacetanilides, which re-
quire multiple steps to synthesize.7 We envisioned a more direct
protocol, which allowed us to avoid preactivation of indoles or
multistep synthesis of indole fragment, that will serve as an alter-
native way to supplement these existing methodologies. Herein,
we report the direct C-3 alkynylation of indoles with aryl-,
cyclohexenyl-substituted 1-bromoalkynes in satisfactory to high
yields under mild conditions.
Ph
Palladium catalyst
base
THF, 50 oC, 24h
+
Br
N
H
N
H
1a
2a
3a
Entry
Catalyst
Base
Yieldb (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
Cul
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
KOAc
NDc
ND
85
ND
ND
89
80
7
ND
ND
ND
<5
Cu(OAc)2
Pd(PPh3)4
Pd(OAc)2
PdCl2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
NEt3
Our initial attempts focused on the coupling of indole (1a)
with 1-bromophenylacetylene (2a),8,9 various conditions were
examined in order to optimize the desired results (Table 1). It
was found that PdCl2(PPh3)2 and Pd(PPh3)4 were effective cata-
lysts compared with Pd(OAc)2 and PdCl2. Under the identical
Cs2CO3
K2CO3
t-BuOK
DMAP
None
<5
a
Reactions were carried out with indole (0.2 mmol), bromophenylacetylene
(0.6 mmol), catalyst (5 mol%), and base (0.4 mmol) in THF (1 mL).
b
Isolated yield after column chromatography.
No desired product was detected by TLC analysis.
* Corresponding author. Tel.: +86 551 3602470; fax: +86 551 3601592.
E-mail address: ygu01@ustc.edu.cn (Y. Gu).
c
0040-4039/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2008.11.097

764
Y. Gu, X. Wang / Tetrahedron Letters 50 (2009) 763–766
Table 2
Pd-catalyzed alkynylation of diverse indolesa
Entry
Heterocycle
Halide
Product
Time (h)
Yieldb (%)
1
24
89
Br
N
H
N
H
3a
2
18
92
Br
N
H
N
H
3b
OMe
3
12
90
MeO
Br
N
H
N
H
3c
Br
Cl
4
22
53
N
H
Cl
N
H
3d
Br
Br
5
24
95
N
H
N
H
3e
6
12
65
N
H
N
H
3f
OMe
7
14
88
MeO
Br
N
N
N
3g
8
14
72
Br
N
3h

Y. Gu, X. Wang / Tetrahedron Letters 50 (2009) 763–766
765
Table 2 (continued)
Entry
Heterocycle
Halide
Product
Time (h)
Yieldb (%)
MeO
MeO
9
24
77
75
Br
Br
N
H
N
H
3i
3j
MeO2C
MeO2C
10
24
N
H
N
H
a
Reactions were carried out with indole (0.5 mmol), bromoalkyne (1.5 mmol), PdCl2(PPh3)2 (10 mol%), and NaOAc (1.0 mmol) in THF (1 mL) at 50 °C.
Isolated yield after column chromatography.
b
was possible that strong base would remove the proton on nitro-
moisture and could be conveniently carried out on the benchtop
using unpurified solvent.13 Most notably, free indoles showed com-
parable reactivity to N-methyl indoles in this transformation; for
example, reaction of indole (1a) with 1-bromophenylacetylene
(2a) provided 3a in 89% isolated yield; no N-alkynylation product
was obtained in this reaction (entry 1). It was found that conjugated
1-bromoalkynes, for example, when the substituents of 1-bro-
moalkynes were aryl or alkenyl groups, the reaction smoothly gave
corresponding alkynylindoles in good to excellent yields (entries
1–6).14 These transformations were also compatible with a diverse
variety of functional groups at 1-bromoalkynes, including alkyl,
methoxy, and chloro groups (entries 2–4). In addition, N-methyl in-
dole proceeded well in this transformation to give corresponding
coupled products (entries 7 and 8). When electron-donating or elec-
tron-withdrawing substituents, such as methoxy or ester groups,
were introduced at 5-position of indole, the reactions occurred in
good yields (entries 9 and 10), Surprisingly, the strong electron-
withdrawing substitute, nitro group was introduced at the same po-
sition, the reaction did not give any coupled product at the same
reaction condition, probably the strong electron-withdrawing group
significantly lowers the nucleophilicity of the indole.
Importantly, these coupling reactions typically provided the 3-
alkynylindoles with high selectivity (>20:1). When C-3 was
blocked (for example, in 3-methylindole), no C-2 substituted
product was observed (Eq. 1). However, when C-2 was blocked
(for example, in 2-methylindole), C-3 alkynylated indole 3k was
obtained in moderate yield,15 probably due to steric effect (Eq.
2). According to our findings, we proposed a possible mechanism
in the C-3 alkynylation of indoles (Scheme 1), which is very similar
to the previous postulated for the palladium-catalyzed arylation of
indoles.3b Direct palladium-catalyzed C–H alkynylation of indole
operates via an electrophilic palladation pathway. Oxidative addi-
tion of alkynyl bromide with palladium catalyst forms alkynylpal-
ladium intermediate 4, which attacks the most electron-rich C-3
position of indole 1 to furnish iminium intermediate 5. Deprotona-
tion of 5 with a base gives the palladium intermediate 6, which
undergoes reductive elimination to provide 3-alkynylindoles 3
and regenerate the palladium catalyst.
gen atom, which altered the electronic distribution of indole aro-
matic ring system and resulted in no occurrence of the desired
reaction.10 Significantly lower yields were obtained when NEt3
and DMAP were used as bases (entries 8 and 12).
With optimized conditions in hand, we embarked on an investi-
gation of the reaction scope (Table 2). In the presence of 10 mol%
of PdCl2(PPh3)2 and 2.0 equiv. of NaOAc in THF, indoles underwent
smooth coupling reaction with bromoalkynes to give only C-3 alky-
nylated products.11,12 This transformation is not sensitive to air and
Ph
PdCl2(PPh)3 (10 mol%)
NaOAc (2.0 equiv.)
+
No Reaction
THF, 50 oC, 24 h
N
H
Br
(1)
Ph
Ph
PdCl2(PPh)3 (10 mol%)
NaOAc (2.0 equiv.)
+
THF, 50 oC, 18 h
N
H
N
H
Br
3k (55% yield)
(2)
R2
B
PdIILn
H
electrophilic substitution
R2 PdIILnBr
N
N
N
R1
4
1
5
R1
R2
Pd0Ln
Br
R2
HB
R2
PdIILn
In conclusion, we have developed a new palladium-catalyzed
method for the direct 3-alkynylation of indoles. These reactions
represent a practical approach to synthesize 3-alkynylindoles with
mild conditions, high regioselectivity and no need to protect indole
nitrogen atom. Ongoing work to expand the substrate scope and
apply this reaction to the synthesis of complex molecules is
underway.
reductive elimination
N
R1
R1
3
6
Scheme 1. Proposed mechanism in the alkynylation of indoles.

766
Y. Gu, X. Wang / Tetrahedron Letters 50 (2009) 763–766
99.2, 91.0, 81.5, 55.4; HRMS (EI) calcd for C17H13NO (M+) 247.0997, found
Acknowledgments
247.0993.
Compound 3d: (53%); IR (KBr)
m 3402, 2207, 1624, 1536, 1465, 1415, 1235,
1097, 747 cmÀ1 1H NMR (300 MHz, CDCl3) d 8.18 (s, 1H, NH), 7.90–7.87 (m,
;
We thank the financial support for this work from the National
Natural Science Foundation of China (No. 20602033) and National
Basic Research Program of China (2006CB922001).
1H), 7.58–7.55 (m, 1H), 7.44–7.39 (m, 2H), 7.32–7.29 (m, 1H), 7.25–7.19 (m,
4H); 13C NMR (75 MHz, CDCl3) d 136.2 (2C), 133.7, 130.2, 129.4 (2C), 129.2,
127.4, 125.0, 124.2, 121.9, 121.1, 112.4, 99.4, 89.7, 89.1; HRMS (EI) calcd for
C16H10NCl (M+) 251.0502, found 251.0498.
Compound 3e: (95%); IR (KBr)
m 3424, 2201, 1634, 1538, 1506, 1456, 1419,
References and notes
1236, 803, 772, 746 cmÀ1 1H NMR (300 MHz, CDCl3) d 8.54 (d, J = 8.4 Hz, 1H),
;
8.15 (s, 1H, NH), 7.93–7.90 (m, 1H), 7.86–7.76 (m, 3H), 7.59 (d, J = 7.8 Hz, 1H),
7.53–7.41 (m, 3H), 7.38–7.32 (m, 1H), 7.27–7.22 (m, 2H); 13C NMR (75 MHz,
CDCl3) d 135.4, 133.4, 133.3, 130.0, 128.6, 128.4, 128.2, 128.1, 126.8, 126.5,
126.4, 125.5, 123.4, 122.0, 121.0, 120.2, 111.6, 99.1, 89.4, 88.2; HRMS (EI) calcd
for C20H13N (M+) 267.1048, found 267.1041.
1. (a) Sundberg, R. J. In Indoles (Best Synthetic Methods); Academic: London, 1996;
pp 1–6; (b) Katritzky, A. R.; Pozharskii, A. F. Handbook of Heterocyclic Chemistry;
Pergamon: Oxford, 2000. Chapter 4; (c) McKay, M. J.; Carroll, A. R.; Quinn, R. J.;
Hooper, J. N. A. J. Nat. Prod. 2002, 65, 595.
2. Cacchi, S.; Fabrizi, G. Chem. Rev. 2005, 105, 2873.
Compound 3f: (65%); IR (KBr)
m 3408, 3058, 2858, 2196, 1617, 1534, 1455, 1417,
3. For recent examples of Pd-catalyzed arylation of indoles, see: (a) Lane, B. S.;
Sames, D. Org. Lett. 2004, 6, 2897; (b) Lane, B. S.; Brown, M. A.; Sames, D. J. Am.
Chem. Soc. 2005, 127, 8050; (c) Bressy, C.; Alberico, D.; Lautens, M. J. Am. Chem.
Soc. 2005, 127, 13148; (d) Deprez, N. R.; Kalyani, D.; Krause, A.; Sanford, M. S. J.
Am. Chem. Soc. 2006, 128, 4972; (e) Wang, X.; Gribkov, D. V.; Sames, D. J. Org.
Chem. 2007, 72, 1476; (f) Dwight, T. A.; Rue, N. R.; Charyk, D.; Josselyn, R.;
DeBoef, B. Org. Lett. 2007, 9, 3137; (g) Stuart, D. R.; Villemure, E.; Fagnou, K. J.
Am. Chem. Soc. 2007, 129, 12072.
4. For recent examples of Pd-catalyzed vinylation of indoles, see: (a) Jia, C.; Lu,
W.; Kitamura, T.; Fujiwara, Y. Org. Lett. 1999, 1, 2097; (b) Ferreira, E. M.; Stoltz,
B. M. J. Am. Chem. Soc. 2003, 125, 95783; (c) Liu, C.; Widenhoefer, R. A. J. Am.
Chem. Soc. 2004, 126, 10250; (d) Grimster, N. P.; Gauntlett, C.; Godfrey, C. R. A.;
Gaunt, M. J. Angew. Chem., Int. Ed. 2005, 44, 3125.
5. Seregin, I. V.; Ryabova, V.; Gevorgyan, V. J. Am. Chem. Soc. 2007, 129, 7742.
6. (a) Yue, D.; Larock, R. C. Org. Lett. 2004, 6, 1037; (b) Zhang, H.; Larock, R. C. J.
Org. Chem. 2002, 67, 7048. and references therein.
7. Arcadi, A.; Cacchi, S.; Fabrizi, G.; Marinelli, F.; Parisi, L. M. J. Org. Chem. 2005, 70,
6213. and references therein.
8. 1-Bromophenylacetylene (2a) was prepared by reaction of phenylacetylene
with silver nitrate and N-bromosuccinimide. See: Li, L.-S.; Wu, Y.-L. Tetrahedron
Lett. 2002, 43, 2427.
9. The reaction of 1-iodophenylacetylene with indole (1a) under various
conditions did not give alkynylated indole, only homocoupled product 1,3-
diyne was observed.
1245, 743 cmÀ1 1H NMR (300 MHz, CDCl3) d 8.13 (s, 1H, NH), 7.73 (d, J = 7.2 Hz,
;
1H), 7.34–7.32 (m, 2H), 7.24–7.14 (m, 2H), 6.21–6.18 (m, 1H), 2.28 (d, J = 1.8 Hz,
2H), 2.16–2.14 (m, 2H), 1.73–1.55 (m, 4H); 13C NMR (75 MHz, CDCl3) d 135.3,
133.8, 128.6, 127.4, 123.1, 121.4, 120.6, 120.1, 111.4, 99.4, 93.0, 80.0, 29.8, 25.9,
22.6, 21.8; HRMS (EI) calcd for C16H15N (M+) 221.1204, found 221.1208.
Compound 3g: (88%); IR (KBr)
m
2928, 2204, 1605, 1564, 1504, 1463, 1382,
1288, 1247, 1176, 1116, 1032, 831, 743 cmÀ1
;
1H NMR (300 MHz, CDCl3) d 7.72
(d, J = 7.8 Hz, 1H), 7.41 (d, J = 8.7 Hz, 2H), 7.24–7.10 (m, 4H), 6.79 (d, J = 8.7 Hz,
2H), 3.73 (s, 3H), 3.67 (s, 3H); 13C NMR (75 MHz, CDCl3) d 159.2, 136.4, 132.8
(2C), 132.0, 129.3, 122.7, 120.3 (2C), 116.6, 114.1 (2C), 109.6, 97.4, 90.8, 81.6,
55.4, 33.1; HRMS (EI) calcd for C18H15NO (M+) 261.1154, found 261.1146.
Compound 3h: (72%); IR (KBr)
m
3053, 2928, 2197, 1723, 1613, 1536, 1469,
1380, 1337, 1251, 1161, 1052, 918, 802, 742, 510, 426 cmÀ1
;
1H NMR (300 MHz,
CDCl3) d 7.72 (d, J = 7.5 Hz, 1H), 7.31–7.15 (m, 4H), 6.18 (br s, 1H), 3.76 (s, 3 H),
2.28 (m, 2 H), 2.16–2.15 (m, 2 H), 1.70–1.57 (m, 4H); 13C NMR (75 MHz, CDCl3) d
136.4, 133.4, 131.8, 129.4, 122.7, 121.5, 120.3, 120.2, 109.5, 99.4, 93.0, 80.2,
33.1, 29.8, 25.9, 22.7, 21.8; HRMS (EI) calcd for C17H17N (M+) 235.1361, found
235.1360.
Compound 3i: (77%); IR (KBr)
m 3415, 2936, 2210, 1485, 1212, 1050, 756,
690 cmÀ1 1H NMR (300 MHz, CDCl3) d 8.14 (s, 1H, NH), 7.59–7.55 (m, 2H), 7.41
;
(d, J = 2.7 Hz, 1H), 7.35–7.21 (m, 5H), 6.90 (dd, J = 6.6, 2.4 Hz, 1H), 3.89 (s, 3H);
13C NMR (75 MHz, CDCl3): d 154.9, 131.3 (2C), 130.3, 129.0, 128.6, 128.3 (2C),
127.6, 124.1, 113.5, 112.2, 101.5, 98.2, 91.2, 83.2, 55.8; HRMS (EI) calcd for
C17H13NO (M+) 247.0997, found 247.0993.
10. Zhang, Z.; Hu, Z.; Yu, Z.; Lei, P.; Chi, H.; Wang, Y.; He, R. Tetrahedron Lett. 2007,
48, 2175.
Compound 3j: (75%); IR (KBr)
m 3435, 2948, 2215, 1692, 1620, 1432, 1273, 1194,
1114, 986, 746, 689 cmÀ1 1H NMR (300 MHz, CDCl3) d 8.57 (s, 1H, NH), 7.94 (d,
;
11. General Procedure: To a mixture of indole (0.5 mmol), PdCl2(PPh3)2 (0.05 mmol,
10 mol %), and NaOAc (1.0 mmol, 2 equiv.) in THF (1.0 mL), bromoalkyne
(1.5 mmol, 3.0 equiv.) was added. The resulting mixture was stirred under 50 °C
until completion (as monitored by TLC). The solvent was removed under
reduced pressure and the residue was purified by flash column chromatography
using petroleum/EtOAc as eluent to afford pure products (3a–j).
J = 8.7 Hz, 1H), 7.57 (d, J = 7.8 Hz, 2 H), 7.49 (d, J = 2.4 Hz, 1H), 7.38–7.30 (m, 3H),
7.28–7.24 (m, 2H), 3.95 (s, 3H); 13C NMR (75 MHz, CDCl3) d 168.3, 138.0, 131.5
(2C), 129.8, 129.4, 128.8, 128.5 (2C), 128.2, 128.0, 124.5, 123.0, 111.5, 100.3,
91.9, 82.2, 52.1; HRMS (EI) calcd for C18H13NO2 (M+) 275.0946, found 275.0946.
12. The structure of 3-phenylethynylindole (3a) was established by 2D NOESY
experiment, which showed cross peak between proton on C-2 at d 7.43 (d,
Compound 3a: (89%); IR (KBr)
m ;
3390, 2214, 1635, 1457, 1237, 747, 689 cmÀ1
J = 2.4 Hz, 1H) and proton on indole nitrogen at
d 8.21 (br s, 1H, NH);
1H NMR (300 MHz, CDCl3) d 8.21 (br s, 1H, NH), 7.84 (d, J = 6.3 Hz, 1H), 7.57 (d,
J = 7.8 Hz, 2H), 7.43 (d, J = 2.4 Hz, 1H), 7.38–7.30 (m, 4H), 7.26–7.20 (m, 2H); 13C
NMR (75 MHz, CDCl3) d 135.4, 131.5 (2C), 128.6, 128.5 (2C), 128.0, 127.7, 124.3,
123.3, 120.9, 120.2, 111.5, 98.9, 91.3, 83.1.
additionally, 2-phenylethynylindole is a known compound, which showed
proton on C-3 at d 6.84 (d, J = 2.4 Hz, 1H). See: Nagamochi, M.; Fang, Y.-Q.;
Lautens, M. Org. Lett. 2007, 9, 2955.
13. When the reaction of indole (1a) with 1-bromophenylacetylene (2a) was
carried out in unpurified THF in the presence of 5% PdCl2(PPh3)2 and 2 equiv.
NaOAc, 88% yield of 3a was obtained.
14. When the substitute of bromoalkyne 2 is alkyl group (e.g., in 1-bromo-1-
octyne), no alkynylated indole was produced, only homocoupled product 1,3-
diyne was observed.
Compound 3b: (92%); IR (KBr)
m
3413, 3059, 2961, 2208, 1618, 1500, 1458,
1416, 1362, 1331, 1260, 834, 744 cmÀ1
;
1H NMR (300 MHz, CDCl3) d 8.20 (br s,
1H, NH), 7.82 (d, J = 6.9 Hz, 1H), 7.50 (d, J = 8.1 Hz, 2H), 7.42 (d, J = 2.7 Hz, 1H),
7.38–7.34 (m, 3H), 7.25–7.18 (m, 2H), 1.30 (s, 9H); 13C NMR (75 MHz, CDCl3) d
151.0, 135.4, 131.2 (2C), 128.7, 127.8, 125.4 (2C), 123.2, 121.3, 120.8, 120.2,
111.5, 99.2, 91.3, 82.3, 34.9, 31.4(3C); HRMS (EI) calcd for C20H19N (M+)
273.1517, found 273.1517.
15. Compound 3k: (55%); IR (KBr)
m 3400, 3057, 2920, 2204, 1597, 1555, 1488,
1457, 1260, 749, 692 cmÀ1 1H NMR (300 MHz, CDCl3) d 7.91 (br s, 1H, NH),
;
Compound 3c: (90%); IR (KBr)
m 3383, 2216, 1605, 1503, 1423, 1247, 836,
7.72–7.69 (m, 1H), 7.57–7.53 (m, 2H), 7.36–7.27 (m, 3H), 7.20–7.13 (m, 3H),
2.48 (s, 3H); 13C NMR (75 MHz, CDCl3) d 139.6, 134.9, 131.4 (2C), 129.3, 128.4
(2C), 127.5, 124.6, 122.3, 120.7, 119.4, 110.7, 96.5, 93.0, 83.4, 12.9; HRMS (EI)
calcd for C17H13N (M+) 231.1048, found 231.1049.
817 cmÀ1 1H NMR (300 MHz, CDCl3) d 8.15 (s, 1H, NH), 7.82 (d, J = 6.6 Hz, 1H),
;
7.50 (d, J = 8.7 Hz, 2H), 7.39 (d, J = 2.7 Hz, 1H), 7.33 (d, J = 6.6 Hz, 1H), 7.26–7.21
(m, 2H), 6.88 (d, J = 8.7 Hz, 2H), 3.81 (s, 3H); 13C NMR (75 MHz, CDCl3) d 159.3,
135.4, 132.9 (2C), 128.6, 127.6, 123.2, 120.8, 120.2, 116.5, 114.1 (2C), 111.5,