Synthesis of Carbazoles via an Intramolecular Cyclization of 2-(6-Substituted 3(Z)-hexen,5-diynyl)anilines and Their Related Molecules

Article abstract of DOI:10.1021/jo0303158

Various 2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines 1a-g were treated with potassium tert-butoxide or potassium 3-ethylpentanoxide in NMP at 60°C for 2 h to give the corresponding 5-substituted carbazoles 2a-g in 36-65% yields together with indoles 9a-g in 21-40% yields, respectively. Exposing the trifluoroacetamide analogues 10h-k under the same reaction conditions gave the carbazoles 2b-e in 37-57% yields and indoles 9b-e in 15-27% yields. Subsequent cyclizations of acetamide analogues 10a-g gave carbazoles 2a-g in 53-86% yields.

Full text of DOI:10.1021/jo0303158

Syn th esis of Ca r ba zoles via a n In tr a m olecu la r Cycliza tion of
2-(6-Su bstitu ted 3(Z)-h exen -1,5-d iyn yl)a n ilin es a n d Th eir Rela ted
Molecu les
Chia-Ying Lee,† Chi-Fong Lin,‡ J eng-Lin Lee,† Ching-Chen Chiu,‡ Wen-Der Lu,† and
Ming-J ung Wu*,‡
Faculty of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan, and
Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical University, Kaohsiung, Taiwan
mijuwu@cc.kmu.edu.tw
Received October 14, 2003
Various 2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines 1a -g were treated with potassium tert-
butoxide or potassium 3-ethylpentanoxide in NMP at 60 °C for 2 h to give the corresponding
5-substituted carbazoles 2a -g in 36-65% yields together with indoles 9a -g in 21-40% yields,
respectively. Exposing the trifluoroacetamide analogues 10h -k under the same reaction conditions
gave the carbazoles 2b-e in 37-57% yields and indoles 9b-e in 15-27% yields. Subsequent
cyclizations of acetamide analogues 10a -g gave carbazoles 2a -g in 53-86% yields.
In tr od u ction
phenanthridinones,5,6 biaryls,5,6 and dibenzofurans.7 In
continuation of the application of anionic cycloaromati-
zation of enediynes, we herein report a new synthesis of
the carbazole nucleus 2 by way of intramolecular cycliza-
tion of 2-(6-substituted 3(Z)-hexen-1,5-diynyl)aniline 1
under alkaline conditions (eq 1).
Carbazoles are a series of natural products which are
widely distributed in higher plants. An important part
of the carbazole alkaloids and their correlative compo-
nents is their variety of biological activities,1 especially
the highlight inhibitory activity of protein kinase C and
topoisomerase.2 Although related works on synthetic and
natural isolated carbarzoles were found in abundance,3
considerable attention is still being paid to the carbazole
alkaloids because of the growing new active structures
and their related studies.4 Recently, we described several
anionic cycloaromatization reactions of conjugated ene-
diyne systems which provided novel methods to prepare
Resu lts a n d Discu ssion
* To whom correspondence should be addressed. Tel: 886-7-3121101
ext 2220. Fax: 886-7-3125339.
The synthesis of 1a is outlined in Scheme 1. Sonogash-
ira coupling reaction8 of cis-dichlorethene (3) with 1-hex-
yne (4) gave vinyl chloride 59 in 50% yield. Compound 5
was then coupled with trimethylsilylacetylene under the
same reaction conditions to give enediyne 6 in 91% yield.
Treatment of 6 with potassium carbonate in dry metha-
nol offered a desilylated product 7a in 79% yield. Finally,
enediyne 7a was coupled with 2-iodoaniline (8) using
tetrakis(triphenylphosphine)palladium as a catalyst to
provide the desired 2-(3(Z)-decen-1,5-diynyl)aniline (1a )
in 39% yield.10
† Graduate Institute of Pharmaceutical Sciences.
‡ Faculty of Medicinal and Applied Chemistry.
(1) (a) Chakraborty, D. P. In The Alkaloids; Bossi, A., Ed.; Academic
Press: New York, 1993; Vol. 44, p 257. (b) Chakraborty, D. P.; Roy, S.
Prog. Chem. Org. Nat. Prod. 1991, 57, 71. (c) Gallagher, P. T. Science
of Synthesis; Thieme: Stuttgart, 2000; Vol. 10, pp 693-744. (d)
Kno¨lker, H. J . In Advances in Nitrogen Heterocycles; Moody, C. J ., Ed.;
J AI: Greenwich, 1995; Vol. 1, p 173. (e) Moody, C. J . Synlett 1994,
681.
(2) (a) Pindur, U.; Kim, Y. S.; Mebrabani, F. Curr. Med. Chem. 1999,
6, 29. (b) Hung, D. T.; J amison, F. T.; Schreiber, S. L. Chem. Biol.
1996, 3, 623. (c) Kleinschroth, J .; Hartenstein, J .; Schaechtete, C.;
Rudolph, C.; Barth, C.; Aranda, J .; Betche, H. J . Ger. Offen. DE
4217964 1993; Chem. Abstr. 1994, 120, 270356c. (d) Omura, S.; Sasaki,
Y.; Iwai, Y.; Takeshima, H. J . Antibiot. 1995, 48, 535.
(3) (a) Hagelin, H.; Oslob, J . D.; Akermark, B. Chem. Eur. J . 1999,
5, 2413. (b) Knolker, H. J . Chem. Soc. Rev. 1999, 28, 151. (c) Pindur,
U.; Erfanian-Abdoust, H. Chem. Rev. 1989, 89, 1681. (d) Grojahn, D.
B.; Vollhardt, K. P. C. J . Am. Chem. Soc. 1986, 108, 2091. (e) Boese,
R.; Van Sickle, A. P.; Vollhardt, K. P. C. Synthesis 1994, 1374.
(4) (a) Silvere, A.; Edwige, N.; Mireille, L.; Cecile, M.; Cao, W.;
Kiefer, D. W.; Sheila, C.; Gerard, L.; Patrice, F. Bioorg. Med. Chem.
Lett. 2002, 12, 209. (b) Istvan, E. J .; Ling, Y.; Kassoum, N.; Tork, T.;
Wu, X.; Cao, Y.; Guo, R.; Li, B.; Zhu, X.; Huang, Y.; Long, Y. Q. J .
Med. Chem. 2001, 44, 4313. (c) Adamczyk, M.; J ohnson, D. D.;
Mattingly, P. G.; Reddy, R. E. Drug. Prepr. Proced. Int. 2001, 33, 505.
(d) Yasuo, K.; Yutaka, A.; Takeshi, S. J . Org. Chem. 2001, 66, 8612.
Several attempts for the conversion of 1a to the
carbazole nucleus 2a have been carried out. Initially,
(5) Wu, M. J .; Lin, C. F.; Lu, W. D. J . Org. Chem. 2002, 67, 5907.
(6) Wu, M. J .; Lin, C. F.; Chen, S. H. Org. Lett. 1999, 1, 767.
(7) Wu, M. J .; Lee, J . Y.; Lin, C. F. Angew. Chem., Int. Ed. 2002,
41, 4077.
(8) Sonogashira, K.; Yatake, T.; Tohda, Y.; Takahashi, S.; Hagihara,
N.; Chem. Commun. 1977, 291.
(9) Chemin, D.; Linstrumelle, G. Tetrahedron 1994, 50, 5335.
(10) Rodriguez, A. L.; Koradin, C.; Dohle, W.; Knochel, P. Angew.
Chem., Int. Ed. 2000, 39, 2488.
10.1021/jo0303158 CCC: $27.50 © 2004 American Chemical Society
Published on Web 02/20/2004
2106
J . Org. Chem. 2004, 69, 2106-2110

Cyclization of 2-(6-Substituted 3(Z)-hexen-1,5-diynyl)anilines
TABLE 2. Cycliza tion of 1a -g w ith P ota ssiu m
ter t-Bu toxid e or P ota siu m 3-Eth yl-3-p en ta n oxid e
SCHEME 1
base
compd
products, yields (%)
t-BuOK
1b, R ) n-C3H7
2b, 51
9b, 26
9c, 21
9d , 25
9e, 23
9f, 40
9g, 31
9a, 24
9b, 28
9c, 25
9d , 20
9e, 26
9f, 30
9g, 27
1c, R ) n-C5H11
1d , R ) n-C6H13
1e, R ) n-C7H15
1f, R ) (CH2)3OTHP
1g, R ) (CH2)4OTHP
1a , R ) n-C4H9
2c, 47
2d , 36
2e, 44
2f, 54
2g, 60
2a , 42
2b, 65
2c, 45
2d , 37
2e, 60
2f, 40
2g, 46
TABLE 1. P r obin g Con d ition s for th e Cycliza tion of 1a
Et3COK
1b, R ) n-C3H7
1c, R ) n-C5H11
1d , R ) n-C6H13
1e, R ) n-C7H15
1f, R ) (CH2)3OTHP
1g, R ) (CH2)4OTHP
TABLE 3. Syn th esis of 10a -k by th e Rea ction of 1 w ith
Acetyl Ch lor id e or Tr iflu or oa cetic An h yd r id e
conditions
products, yields (%)
9a , 40
Na, MeOH, reflux, 16 h
n-BuLi, THF, 60 °C, 16 h
t-BuOK, NMP, 60 °C, 2 h
no desired product
2a , 58
9a , 21
2-(3(Z)-decen-1,5-diynyl)aniline (1a ) was treated with
sodium methoxide in refluxing methanol for 16 h to give
an indole product 9a in 40% yield; however, no desired
carbazole 2a was obtained (Table 1). Treatment of 1a
with n-BuLi in THF at 60 °C yielded neither the carba-
zole nor indole. However, treatment of compound 1a with
t-BuOK in NMP11 at 60 °C for 2 h afforded 5-substituted
carbazole 2a in a yield of 58% together with indole
product 9a in a yield of 21%.
methoda
A
compd
products, yields (%)
R1 ) COCH3 10a , 58
1a , R ) n-C4H9
1b, R ) n-C3H7
1c, R ) n-C5H11
1d , R ) n-C6H13
1e, R ) n-C7H15
1f, R ) (CH2)3OTHP
1g, R ) (CH2)4OTHP
1a , R ) n-C4H9
1c, R ) n-C5H11
1d , R ) n-C6H13
1e, R ) n-C7H15
10b, 97
10c, 98
10d , 64
10e, 78
10f, 57
10g, 55
10h , 78
10i, 67
10j, 76
10k , 90
After the successful investigation of the synthesis of
5-substituted carbazoles, we then turned our attention
to test the generality of this cyclization reaction. Various
2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines 1b-g were
prepared by the described method. Treatment of 1b-g
with t-BuOK under the same reaction conditions resulted
in the formation of carbazoles 2b-g in yields of 36-60%
and indoles 9b-g in 21-40% yield (Table 2). It was
thought that the formation of the indoles could be due
to the fast protonation during the cyclization process, and
the employment of a more bulky base could reduce the
rate of protonation process and would allow us to obtain
the higher yield of carbazoles. Thus, potassium 3-ethyl-
pentanoxide was introduced to this double cyclization
reaction. The results are shown in Table 2. Treatment
of 1a -g with potassium 3-ethylpentanoxide in NMP at
60 °C for 2 h formed carbazoles 2a -g as the major
products in 37-65% yields together with indoles 9a -g
as minor products in 20-30% yields. It seems that there
is no significant alternation of the product formation by
using potassium 3-ethylpentanoxide as a base. The
indoles are still obtained as the minor product. Despite
this, carbazoles were the major products of double
cyclization reaction of 2-(6-substituted 3(Z)-hexen-1,5-
diynyl)anilines 1a -g.
B
R1 ) COCF3
a
Conditions: (method A) CH3COCl, Et3N, CH2Cl2, 25 °C, 2 h;
(method B) (CF3CO)2O, Et3N, CH2Cl2, 25 °C, 2 h.
To diminish the formation of indoles, we then turned
our attention to the cyclization of N-acetyl-2-(6-substi-
tuted 3(Z)-hexen-1,5-diynyl)anilines 10a -g. Compounds
10a -g were prepared by reaction of 1a -g with acetyl
chloride (Table 3), and treatment of 10a -g with t-BuOK
in NMP at 60 °C for 2 h gave the carbazoles 2a -g in
45-86% yields. Only trace amount of indoles were
observed using TLC in some cases. The trifluoroaceta-
mide analogues 10h -k were also prepared (Table 3), and
treatment of 10h -k with t-BuOK under the same reac-
tion conditions produced the carbazoles 2b-e in 37-57%
yields and indoles 9b-e in 15-27% yields, respectively
(Table 4). The results are similar to that of cyclization of
1b-e. This possibly because the trifluoroacetyl group is
more labile than the acetyl group under these reaction
conditions. We also have the phenylsulfonamide analogue
J . Org. Chem, Vol. 69, No. 6, 2004 2107

Lee et al.
TABLE 4. Cycliza tion of 10a -k w ith t-Bu OK
) 7.2, 1.6 Hz, 1H), 6.73-6.64 (m, 2H), 6.05 (d, J ) 10.6 Hz,
1H), 5.89 (dt, J ) 10.6, 2.2 Hz, 1H), 4.43 (bs, 2H), 2.47 (td, J
) 6.6, 2.2 Hz, 2H), 1.62-1.43 (m, 4H), 0.92 (t, J ) 2.2 Hz,
3H); 13C NMR (CDCl3, 50 MHz) δ 148.0, 131.9, 130.0, 119.2,
118.3, 117.7, 114.1, 107.7, 98.9, 93.1, 92.9, 78.9, 30.8, 22.0, 19.6,
13.6; HRMS (EI) calcd for C16H17N 223.1362, found 223.1359.
2-(6-P r op yl-3(Z)-h exen -1,5-d iyn yl)a n ilin e (1b): 1H NMR
(CDCl3, 200 MHz) δ 7.31 (dt, J ) 8.4, 0.8 Hz, 1H), 7.18 (td, J
) 7.0, 1.6 Hz, 1H), 6.74-6.65 (m, 2H), 6.06 (d, J ) 10.6 Hz,
1H), 5.89 (dt, J ) 10.6, 2.2 Hz, 1H), 4.18 (bs, 2H), 2.46 (td, J
) 7.0, 2.2 Hz, 2H), 1.62 (sext, J ) 7.0 Hz, 2H), 1.03 (t, J ) 7.2
Hz, 3H); 13C NMR (CDCl3, 50 MHz) δ 148.0, 131.9, 129.9,
119.1, 118.3, 117.7, 114.1, 107.7, 98.8, 93.1, 92.9, 79.1, 29.7,
22.2, 13.6; HRMS (EI) calcd for C15H15N 209.1206, found
209.1211.
2-(6-P en tyl-3(Z)-h exen -1,5-d iyn yl)a n ilin e (1c): 1H NMR
(CDCl3, 200 MHz) δ 7.31 (dt, J ) 7.6, 0.6 Hz, 1H), 7.17 (td, J
) 7.2, 1.6 Hz, 1H), 6.73-6.64 (m, 2H), 6.05 (d, J ) 10.8 Hz,
1H), 5.89 (dt, J ) 10.8, 2.2 Hz, 1H), 4.44 (bs, 2H), 2.47 (td, J
) 7.2, 2.2 Hz, 2H), 1.60 (sext, J ) 7.0 Hz, 2H), 1.43-1.22 (m,
4H), 0.93 (t, J ) 7.0 Hz, 3H); 13C NMR (CDCl3, 50 MHz) δ
147.9, 131.9, 129.9, 119.1, 118.3, 117.7, 114.1, 107.7, 99.0, 92.9,
92.9, 78.9, 31.1, 28.5, 22.2, 19.8, 13.6; HRMS (EI) calcd for
compd
R1
R2
yield (%)
2a , 65
10a
10b
10c
10d
10e
10f
10g
10h
10i
COCH3
n-C4H9
n-C3H7
2b, 86
2c, 77
2d , 53
2e, 80
2f, 53
2g, 45
2a , 44
2c, 44
2d , 40
2e, 80
n-C5H11
n-C6H13
n-C7H15
(CH2)3OTHP
(CH2)4OTHP
n-C4H9
n-C5H11
n-C6H13
n-C7H15
COCF3
9a , 15
9c, 15
9d , 27
9e, 24
10j
10k
C
17H19N 237.1519, found 237.1519.
2-(6-Hexyl-3(Z)-h exen -1,5-d iyn yl)a n ilin e (1d ): 1H NMR
of 1a , but cyclization of this derivative gave a very
complicated product mixture.
(CDCl3, 200 MHz) δ 7.33 (dd, J ) 7.6, 1.4 Hz, 1H), 7.19 (td, J
) 8.0, 1.4 Hz, 1H), 6.76 (td, J ) 8.0, 2.2 Hz, 2H), 6.07 (d, J )
10.8 Hz, 1H), 5.91 (dt, J ) 10.8, 2.2 Hz, 1H), 3.80 (bs, 2H),
2.49 (td, J ) 6.8, 2.2 Hz, 2H), 1.65-1.28 (m, 8H), 0.94 (t, J )
6.6 Hz, 3H); 13C NMR (CDCl3. 50 MHz) δ 148.0, 131.9, 129.9,
119.1, 118.3, 117.7, 114.1, 107.7, 99.0, 92.9, 92.9, 78.9, 31.5,
Con clu sion
In conclusion, we have examined several reaction
conditions for the synthesis of 5-substituted carbazoles
by way of intramolecular anionic cyclization of 2-(6-
substituted 3(Z)-hexen-1,5-diynyl)anilines. Among them,
the optimal condition to generate the carbazoles is the
cyclization of N-acetyl-2-(6-substituted 3(Z)-hexen-1,5-
diynyl)anilines. The results strongly enhance the syn-
thetic application of anionic cycloaromatization of ene-
diynes.
28.7, 28.6, 22.2, 19.8, 13.6; HRMS (EI) calcd for C18H21
251.1675, found 251.1675.
N
2-(6-Hep tyl-3(Z)-h exen -1,5-d iyn yl)a n ilin e (1e): 1H NMR
(CDCl3, 200 MHz) δ 7.31 (dt, J ) 7.6, 0.8 Hz, 1H), 7.17 (td, J
) 7.4, 1.6 Hz, 1H), 6.73-6.64 (m, 2H), 6.05 (d, J ) 10.6 Hz,
1H), 5.89 (dt, J ) 10.6, 2.2 Hz, 1H), 4.44 (bs, 2H), 2.47 (td, J
) 6.8, 2.0 Hz, 2H), 1.57 (sext, J ) 7.0 Hz, 2H), 1.45-1.27 (m,
8H), 0.88 (t, J ) 6.8 Hz, 3H); 13C NMR (CDCl3, 50 MHz) δ
148.0, 131.9, 129.9, 119.2, 118.3, 117.7, 114.1, 107.7, 99.0, 93.1,
92.9, 78.9, 31.7, 29.7, 28.9, 28.8, 22.6, 19.9, 14.0; HRMS (EI)
calcd for C19H23N 265.1832, found 265.1830.
Exp er im en ta l Section
2-(9-Te t r a h yd r op ya n yloxy-3(Z)-n on e n -1,5-d iyn yl)-
a n ilin e (1f): H NMR (CDCl3, 200 MHz) δ 7.31 (dd, J ) 8.0,
Gen er a l P r oced u r e for th e Cycliza tion of 2-(6-Su bsti-
tu ted 3(Z)-h exen -1,5-d iyn yl)a n ilin es or N-Acetyla n ilin es
(Ba se A). To a stirred solution of 2-(6-substituted 3(Z)-hexen-
1,5-diynyl)anilines or N-acetylanilines (1 mmol) in 10 mL of
NMP was added t-BuOK (2.5 mmol), and the solution was
heated to 60 °C and stirred for 2 h. After the solution was
cooled to room temperature, a saturated aqueous solution of
NaCl was added into the reaction mixture and extracted with
EtOAc. The combined organic extracts were dried over anhy-
drous MgSO4. After filtration and removal of solvent, the
residue was purified by column chromatography (silica gel,
hexane as eluent) to give the products. Ba se B: The reaction
conditions were as the same as the above conditions, except
t-BuOK was replaced with potassium 3-ethylpentanoxide.
Gen er a l P r oced u r e for th e P r ep a r a tion of N-Acetyl-
2-(6-su bstitu ted 3(Z)-h exen -1,5-d iyn yl)a n ilin es a n d Th eir
Rela ted Der iva tive fr om 2-(6-Su bstitu ted 3(Z)-h exen -1,5-
d iyn yl)a n ilin es (Ba se A). To a solution of 2-(6-substituted
3(Z)-hexen-1,5-diynyl)anilines (1 mmol) in 10 mL of CH2Cl2
were added acetyl chloride (1.2 mmol) and triethylamine (1.5
mmol), and the solution was stirred for 4 h. Then, saturated
aqueous NaCl solution was added and the mixture extracted
with CH2Cl2. The combined organic extracts were dried over
anhydrous MgSO4. After filtration and removal of solvent, the
residue was purified by column chromatography to give the
products. Ba se B: The reaction conditions were the same as
above, except the acetyl chloride was replaced by trifluoroacetic
anhydride (1.2 mmol).
1
1.4 Hz, 1H), 7.18 (td, J ) 7.4, 1.8 Hz, 1H), 6.75-6.00 (m, 2H),
5.88-5.82 (m, 2H), 4.58 (bs, 2H), 3.90-3.79 (m, 2H), 3.54-
3.46 (m, 2H), 2.90 (bs, 2H), 2.59 (td, J ) 7.2, 2.2 Hz, 2H), 1.91-
1.22 (m, 8H); 13C NMR (CDCl3, 50 MHz) δ 153.6, 148.2, 131.8,
130.0, 119.1, 118.5, 117.6, 115.1, 106.5, 99.0, 93.1, 79.3, 66.0,
62.5, 30.7, 29.0, 25.4, 19.6, 16.7, 13.9; HRMS (EI) calcd for
C
19H23N 309.1729, found 309.1724.
2-(9-Te t r a h yd r op ya n yloxy-3(Z)-d e ce n -1,5-d iyn yl)-
1
a n ilin e (1g): H NMR (CDCl3, 200 MHz) δ 7.29 (dt, J ) 7.4,
1.6 Hz, 1H), 7.15 (td, J ) 7.4, 1.6 Hz, 1H), 6.70-6.61 (m, 2H),
6.04 (d, J ) 10.6 Hz, 1H), 5.87 (dt, J ) 10.6, 2.2 Hz, 1H), 4.55-
(t, J ) 1.8 Hz, 1H), 3.92-3.70 (m, 2H), 3.52-3.39 (m, 2H),
2.49-2.43 (m, 2H), 1.81-1.52 (m, 10H); 13C NMR (CDCl3. 50
MHz) δ 153.7, 148.3, 131.9, 130.1, 119.1, 118.5, 117.7, 114.1,
107.6, 99.1, 93.2, 79.4, 67.1, 62.7, 30.9, 29.1, 28.9, 25.8, 25.6,
19.9, 14.0; HRMS (EI) calcd for C19H23N 323.1885, found
323.1883.
1
4-Bu tyl-9H-ca r ba zole (2a ): H NMR (C6D6, 400 MHz) δ
8.36 (d, J ) 8.8 Hz, 1H), 8.29 (d, J ) 8.4 Hz, 1H), 7.8 (td, J )
6.8, 0.4 Hz, 1H), 7.64-7.54 (m, 2H), 7.54 (s, 1H), 6.95 (dd, J )
6.4, 2.8 Hz, 1H), 6.28 (dd, J ) 6.8, 1.2 Hz, 1H), 3.21 (t, J ) 7.6
Hz, 2H), 1.88 (quint, J ) 7.2 Hz, 2H), 1.60 (sext, J ) 7.2 Hz,
2H), 1.05 (t, J ) 7.2 Hz, 3H); 13C NMR (C6D6, 100 MHz) δ
142.9, 139.5, 131.7, 123.2, 122.3, 121.6, 120.3, 118.2, 116.6,
108.2, 94.4, 34.9, 29.8, 23.2, 14.8; HRMS (EI) calcd for C15H15
223.1362, found 223.1361.
N
2-(6-Bu tyl-3(Z)-h exen -1,5-d iyn yl)a n ilin e (1a ): 1H NMR
(CDCl3, 200 MHz) δ 7.31 (dt, J ) 7.4, 0.6 Hz, 1H), 7.17 (td, J
4-P r op yl-9H-ca r ba zole (2b): 1H NMR (C6D6, 400 MHz) δ
8.10 (d, J ) 8.8 Hz, 1H), 7.83 (d, J ) 8.0 Hz, 1H), 7.38 (t, J )
2108 J . Org. Chem., Vol. 69, No. 6, 2004

Cyclization of 2-(6-Substituted 3(Z)-hexen-1,5-diynyl)anilines
7.6 Hz, 2H), 7.27 (td, J ) 6.8, 2.4 Hz, 1H), 6.86 (dd, J ) 6.8,
2.4 Hz, 1H), 6.75 (s, 1H), 6.29 (d, J ) 6.8 Hz, 1H), 3.31 (t, J )
7.0 Hz, 2H), 1.93 (sext, J ) 7.2 Hz, 2H), 0.86 (t, J ) 6.8 Hz,
3H); 13C NMR (C6D6, 100 MHz) δ 141.8, 138.5, 130.3, 130.2,
122.1, 121.6, 120.3, 119.2, 117.2, 115.4, 107.8, 92.8, 36.5, 20.3,
13.7; HRMS (EI) calcd for C16H17N 209.1206, found 209.1199.
J ) 16.4 Hz, 1H), 6.33 (s, 1H), 5.82 (dt, J ) 16.4, 2.4 Hz, 1H),
2.28 (td, J ) 7.2, 2.0 Hz, 2H), 1.51-1.19 (m, 6H), 0.87 (t, J )
7.2 Hz, 3H); 13C NMR (C6D6, 100 MHz) δ 136.3, 131.4, 131.2,
123.9, 121.9, 121.2, 111.8, 108.3, 105.0, 102.7, 94.6, 81.1, 29.7,
28.4, 22.2, 19.7, 14.2; HRMS (EI) calcd for C17H19N 237.1518,
found 237.1514.
1
1
4-P en tyl-9H-ca r ba zole (2c): H NMR (C6D6, 400 MHz) δ
2-Dec-1-en -3-yn yl-1H-in d ole (9d ): H NMR (CDCl3, 200
8.12 (d, J ) 8.4 Hz, 1H), 7.84 (d, J ) 8.0 Hz, 1H), 7.40 (t, J )
7.2 Hz, 2H), 7.27 (td, J ) 6.8, 1.2 Hz, 1H), 6.86 (dd, J ) 7.6,
2.4 Hz, 1H), 6.76 (s, 1H), 6.29 (d, J ) 6.8 Hz, 1H), 3.33 (t, J )
7.6 Hz, 2H), 1.94-1.90 (m, 2H), 1.88-1.87 (m, 2H), 1.60-1.54
(m, 2H), 1.53-1.41 (m, 2H), 0.81 (t, J ) 7.2 Hz, 3H); 13C NMR
(C6D6. 100 MHz) δ 142.1, 138.5, 130.3, 130.2, 122.1, 121.6,
120.3, 119.2, 117.1, 115.4, 107.6, 92.8, 34.6, 31.5, 26.8, 22.5.3,
14.0; HRMS (EI) calcd for C17H19N 237.1518, found 237.1525.
MHz) δ 8.11 (s, 1H), 7.56 (td, J ) 6.0, 0.8 Hz, 1H), 7.32 (dd, J
) 8.0, 0.8 Hz, 1H), 7.20 (td, J ) 7.6, 1.2 Hz, 1H), 7.09 (td, J )
6.0, 1.2 Hz, 1H), 6.87 (d, J ) 1 6.4 Hz, 1H), 6.54 (d, J ) 1.6
Hz, 1H), 5.97 (dt, J ) 16.4, 2.4 Hz,1H), 2.40 (td, J ) 7.2, 2.4
Hz, 2H), 1.70-1.07 (m, 8H), 0.84 (t, J ) 7.8 Hz, 3H); 13C NMR
(CDCl3, 50 MHz) δ 148.8, 141.3, 139.7, 128.5, 126.5, 122.7,
121.9, 121.1, 120.2, 111.6, 110.3, 96.8, 34.9, 31.9, 31.7, 29.4,
22.6, 14.1; HRMS (EI) calcd for C18H21N 251.1675, found
251.1679.
1
4-Hexyl-9H-ca r ba zole (2d ): H NMR (C6D6, 200 MHz) δ
2-Un d ec-1-en -3-yn yl-1H-in d ole (9e): 1H NMR (C6D6, 400
MHz) δ 7.54 (d, J ) 7.2 Hz, 1H), 7.21-7.16 (m, 3H), 7.13 (td,
J ) 6.8 Hz, 1H), 7.02 (dd, J ) 8.4, 0.8 Hz, 1H), 6.85 (d, J )
16.4 Hz, 1H), 6.33 (s, 1H), 5.83 (dt, J ) 16, 2.4 Hz, 1H), 2.32
(dt, J ) 6.8 Hz, 2.0 Hz, 2H), 1.64-1.51 (m, 2H), 1.49-1.20
(m, 8H), 0.92 (t, J ) 7.2 Hz, 3H); 13C NMR (C6D6, 100 MHz) δ
138.2, 136.3, 131.2, 123.9, 130.0, 123.9, 121.9, 121.2, 111.7,
108.3, 105.0, 94.6, 81.1, 32.8, 30.8, 29.9, 23.7, 21.2, 20.8, 14.9;
HRMS (EI) calcd for C19H23N 265.1832, found 265.1834.
2-[7-(Tet r a h yd r op yr a n -2-yloxy)h ep t -1-en -3-yn yl]-1H -
8.38 (d, J ) 8.8 Hz, 1H), 8.29 (d, J ) 8.0 Hz, 1H), 7.79 (t, J )
7.2 Hz, 1H), 7.64-7.54 (m, 2H), 6.96 (t, J ) 6.4 Hz, 1H), 6.30
(d, J ) 6.4 Hz, 1H), 3.23 (t, J ) 7.6 Hz, 2H), 1.91-1.85 (m,
2H), 1.74-1.47 (m, 6H), 0.82 (t, J ) 7.2 Hz, 3H); 13C NMR
(C6D6, 50 MHz) δ 142.9, 139.5, 131.7, 131.6, 123.3, 122.3, 121.6,
120.3, 118.2, 116.5, 108.2, 94.4, 35.3, 32.5, 29.8, 27.7, 23.5, 14.9;
HRMS (EI) calcd for C18H21N 251.1675, found 251.1672.
4-Hep tyl-9H-ca r ba zole (2e): 1H NMR (C6D6, 200 MHz) δ
8.12 (d, J ) 8.4 Hz, 1H), 7.84 (d, J ) 7.0 Hz, 1H), 7.45-7.22
(m, 3H), 6.94 (t, J ) 7.0 Hz, 1H), 6.35 (d, J ) 6.2 Hz, 1H),
3.35 (t, J ) 7.6 Hz, 2H), 1.94-1.82 (m, 2H), 1.61-1.19 (m, 8H),
0.89 (t, J ) 6.8 Hz, 3H); 13C NMR (C6D6, 100 MHz) δ 142.1,
138.6, 132.1, 131.1, 122.0, 121.7, 120.3, 119.2, 117.1, 115.4,
107.6, 92.8, 34.6, 31.7, 29.7, 29.3, 27.1, 22.6, 14.1; HRMS (EI)
calcd for C19H23N 265.1832, found 265.1828.
4-[3-(Tet r a h yd r op yr a n -2-yloxy)p r op yl]-9H -ca r b a zole
(2f): 1H NMR (C6D6, 400 MHz) δ 8.26 (d, J ) 8.8 Hz, 1H),
7.92 (d, J ) 8.0 Hz, 1H), 7.44 (t, J ) 7.6 Hz, 1H), 7.29 (dd, J
) 7.6, 1.6 Hz, 1H), 7.26 (d, J ) 1.2 Hz, 1H), 6.79 (s, 1H), 6.57
(dd, J ) 6.4, 2.8 Hz, 1H), 5.96 (d, J ) 6.0 Hz, 1H), 4.55 (t, J )
3.2 Hz, 1H), 3.81-3.74 (m, 2H), 3.43-3.39 (m, 1H), 3.28-3.22
(m, 1H), 3.13-3.04 (m, 2H), 1.85-1.77 (m, 2H), 1.65-1.59 (m,
2H), 1.40-1.23 (m, 4H); 13C NMR (C6D6, 100 MHz) δ 142.6,
139.4, 131.7, 131.6, 123.3, 122.3, 121.5, 120.4, 118.3, 116.9,
108.6, 99.3, 94.5, 66.9, 62.3, 32.3, 31.7, 28.4, 26.6, 20.9; HRMS
(EI) calcd for C20H23NO2 309.1729, found 309.1730.
4-[3-(Tetr ah ydr opyr an -2-yloxy)bu tyl]-9H-car bazole (2g):
1H NMR (C6D6, 400 MHz) δ 8.10 (d, J ) 8.4 Hz, 1H), 7.80 (d,
J ) 8.4 Hz, 1H), 7.45-7.31 (m, 3H), 7.24-7.18 (m, 1H), 6.72
(s, 1H), 6.28 (d, J ) 6.4 Hz, 1H), 4.58 (t, J ) 4.4 Hz, 1H), 3.86-
3.81 (m, 2H), 3.50-3.44 (m, 2H), 3.37 (t, J ) 7.2 Hz, 2H), 2.02-
1.86 (m, 2H), 1.85-1.71 (m, 2H), 1.69-1.47 (m, 6H); 13C NMR
(C6D6, 100 MHz) δ 142.1, 131.7, 130.2, 128.3, 122.2, 121.8,
120.3, 119.3, 117.3, 115.5, 107.8, 99.0, 67.2, 62.5, 31.6, 30.6,
29.7, 25.4, 19.7; HRMS (EI) calcd for C21H25NO2 323.1885,
found 323.1878.
2-Oct-1-en -3-yn yl-1H-in d ole (9a ): 1H NMR (CDCl3, 200
MHz) δ 8.09 (s, 1H), 7.57 (d, J ) 7.6 Hz, 1H), 7.34 (d, J ) 7.0
Hz, 1H), 7.22 (t, J ) 6.8 Hz, 1H), 7.18 (t, J ) 7.0 Hz, 1H), 6.89
(d, J ) 16.2 Hz, 1H), 6.53 (s, 1H), 5.98 (dt, J ) 16.2, 2.2 Hz,
1H), 2.42 (td, J ) 6.8, 1.8 Hz, 2H), 1.59-1.33 (m, 4H), 0.88 (t,
J ) 7.8 Hz, 3H); 13C NMR (CDCl3, 50 MHz) δ 138.5, 128.7,
128.3, 123.2, 120.8, 120.3, 110.6, 107.1, 103.9, 94.1, 79.8, 29.7,
22.0, 19.4, 13.6; HRMS (EI) calcd for C15H15N 223.1362, found
223.1350.
1
in d ole (9f): H NMR (CDCl3, 400 MHz) δ 8.29 (s, 1H), 7.58
(d, J ) 7.6 Hz, 1H), 7.32 (dd, J ) 8.8, 0.8 Hz, 1H), 7.21 (td, J
) 8.0, 0.8 Hz, 1H), 7.11 (td, J ) 7.2, 1.2 Hz, 1H), 6.86 (d, J )
8.0 Hz, 1H), 6.54 (t, J ) 2.8 Hz, 1H), 5.96 (dt, J ) 4.4, 2.0 Hz,
1H), 4.76 (t, J ) 2.8 Hz, 1H), 3.95-3.87 (m, 2H), 3.57-3.52
(m, 2H), 2.55 (td, J ) 6.8, 2.0 Hz, 2H), 1.92-1.73 (m, 4H),
1.65-1.53 (m, 4H); 13C NMR (CDCl3, 100 MHz) δ 136.9, 135.4,
130.3, 128.7, 123.1, 120.7, 120.2, 110.7, 106.9, 103.9, 93.1, 79.8,
65.9, 62.2, 30.7, 29.6, 28.9, 25.4, 19.5, 16.6; HRMS (EI) calcd
for C20H23NO2 309.1729, found 309.1721.
2-[8-(Tetr a h yd r op yr a n -2-yloxy)oct-1-en -3-yn yl]-1H-in -
1
d ole (9g): H NMR (CDCl3, 400 MHz) δ 8.28 (s, 1H), 7.56 (d,
J ) 8.0 Hz, 1H), 7.30 (dd, J ) 8.4, 0.8 Hz, 1H), 7.19 (td, J )
8.0, 0.8 Hz, 1H), 7.13 (td, J ) 7.6, 1.6 Hz, 1H), 6.84 (d, J ) 8.4
Hz, 1H), 6.52 (t, J ) 2.8 Hz, 1H), 5.92 (dt, J ) 4.8, 2.4 Hz,
1H), 4.75 (t, J ) 2.8 Hz, 1H), 3.90-3.78 (m, 2H), 3.54-3.48
(m, 2H), 2.53 (td, J ) 7.2, 2.4 Hz, 2H), 1.90-1.71 (m, 6H),
1.65-1.53 (m, 4H); 13C NMR (CDCl3, 100 MHz) δ 136.8, 135.3,
130.1, 128.6, 123.1, 120.7, 120.1, 110.5, 107.1, 103.8, 92.9, 79.5,
65.8, 62.3, 30.9, 29.5, 28.9, 25.4, 19.5, 16.6, 14.1; HRMS (EI)
calcd for C21H25NO2 323.1885, found 323.1881.
N-Acetyl-2-(6-bu tyl-3(Z)-h exen -1,5-d iyn yl)a n ilin e (10a ):
1H NMR (CDCl3, 200 MHz) δ 8.43 (d, J ) 8.8 Hz, 1H), 8.09 (s,
1H), 7.35-7.29 (m, 2H), 7.08 (td, J ) 7.8, 1.2 Hz, 1H), 5.98
(dd, J ) 3.6,1.8 Hz, 2H), 2.45 (td, J ) 7.0, 1.8 Hz, 2H), 2.23 (s,
3H), 1.63-1.33 (m, 2H), 0.92 (t, J ) 7.0 Hz, 3H); 13C NMR
(CDCl3, 50 MHz) δ 168.2, 138.8, 131.5, 129.8, 123.3, 120.9,
119.2, 116.9, 111.7, 99.9, 94.1, 90.7, 78.6, 31.1, 28.4, 22.1, 21.9,
13.7; HRMS (EI) calcd for C18H19NO 265.1467, found 265.1475.
N-Acetyl-2-(6-pr opyl-3(Z)-h exen -1,5-diyn yl)an ilin e (10b):
1H NMR (CDCl3, 200 MHz) δ 8.56 (d, J ) 8.0 Hz, 1H), 8.24 (s,
1H), 7.57-7.39 (m, 2H), 7.21 (td, J ) 7.2, 1.0 Hz, 1H), 6.13
(dd, J ) 3.8, 1.6 Hz, 2H), 2.56 (td, J ) 7.2 Hz, 2H), 2.36 (s,
3H), 1.78-1.63 (m, 2H), 1.07 (t, J ) 6.6 Hz, 3H); 13C NMR
(CDCl3, 50 MHz) δ 169.8, 138.9, 131.6, 129.9, 123.8, 123.3,
120.9, 119.2, 117.1, 99.8, 94.1, 90.7, 78.6, 28.4, 22.1, 21.9, 13.5;
HRMS (EI) calcd for C17H17NO2 251.1310, found 251.1304.
N-Acetyl-2-(6-pen tyl-3(Z)-h exen -1,5-diyn yl)an ilin e (10c):
1H NMR (CDCl3, 200 MHz) δ 8.43 (d, J ) 8.0 Hz, 1H), 8.11 (s,
1H), 7.44-7.29 (m, 2H), 7.08 (td, J ) 7.8, 1.2 Hz, 1H), 6.05-
5.91 (m, 2H), 2.45 (td, J ) 6.8, 1.8 Hz, 2H), 2.24 (s, 3H), 1.64-
2-Hep t-1-en -3-yn yl-1H-in d ole (9b): 1H NMR (CDCl3, 200
MHz) d 8.10 (s, 1H), 7.56 (d, J ) 7.8 Hz, 1H), 7.36 (d, J ) 7.2
Hz, 1H), 7.20 (t, J ) 7.0 Hz, 1H), 7.15 (t, J ) 7.2 Hz, 1H), 6.87
(d, J ) 16.2 Hz, 1H), 6.51 (s, 1H), 5.97 (dt, J ) 16.2, 2.2 Hz,
1H), 2.40 (td, J ) 7.0, 1.8 Hz, 2H), 1.56-1.31 (m, 2H), 0.89 (t,
J ) 7.8 Hz, 3H); 13C NMR (CDCl3, 50 MHz) δ 139.1, 129.2,
128.5, 123.5, 120.7, 120.3, 110.5, 107.1, 103.7, 93.9, 79.9, 36.1,
21.1, 13.5; HRMS calcd for C16H17N 209.1206, found 209.1208.
2-Non -1-en -3-yn yl-1H-in d ole (9c): 1H NMR (C6D6, 400
MHz) δ 7.54 (d, J ) 8.0 Hz, 1H), 7.22 (dt, J ) 8.4, 2.8 Hz, 1H),
7.19 (td, J ) 8.0, 0.8 Hz, 1H), 7.11 (t, J ) 7.6 Hz, 1H), 6.84 (d,
1.50 (m, 2H), 1.46-1.30 (m, 4H), 0.87 (t, J ) 7.6 Hz, 3H); 13
C
NMR (CDCl, 50 MHz) δ 168.1, 138.8, 131.5, 129.8, 123.2, 120.9,
119.1, 116.9, 111.7, 99.9, 94.0, 90.6, 78.4, 30.9, 28.3, 22.1, 22.1,
19.9, 13.8; HRMS (EI) calcd for C21H25NO2 279.1623, found
279.1620.
J . Org. Chem, Vol. 69, No. 6, 2004 2109

Lee et al.
N-Acetyl-2-(6-h exyl-3(Z)-h exen -1,5-diyn yl)an ilin e (10d):
1H NMR (CDCl3, 200 MHz) δ 8.43 (d, J ) 8.2 Hz, 1H), 8.11 (s,
1H), 7.44-7.30 (m, 2H), 7.08 (td, J ) 7.6, 0.8 Hz, 1H), 6.04-
5.92 (m, 2H), 2.44 (td, J ) 7.0, 1.4 Hz, 2H), 2.23 (s, 3H), 1.61-
1.23 (m, 8H), 0.85 (t, J ) 6.8 Hz, 3H); 13C NMR (CDCl3, 50
MHz) δ 168.1, 138.8, 131.5, 129.8, 123.2, 120.9, 119.1, 116.9,
111.7, 99.9, 94.0, 90.7, 78.5, 31.2, 28.6, 28.5, 24.7, 22.4, 19.9,
13.9; HRMS (EI) calcd for C21H25NO2 293.1780, found 293.1772.
N-Acetyl-2-(6-h eptyl-3(Z)-h exen -1,5-diyn yl)an ilin e (10e):
1H NMR (CDCl3, 200 MHz) δ 8.43 (d, J ) 8.2 Hz, 1H), 8.11 (s,
1H), 7.43-7.29 (m, 2H), 7.07 (td, J ) 7.6, 1.4 Hz, 1H), 6.04-
5.91 (m, 2H), 2.44 (td, J ) 6.6, 1.4 Hz, 2H), 2.23 (s, 3H), 1.59-
1.21 (m, 10H), 0.87 (t, J ) 7.0 Hz, 3H); 13C NMR (CDCl3, 50
MHz) δ 168.1, 138.8, 131.5, 129.9, 123.3, 121.0, 119.2, 117.0,
111.7, 99.9, 94.1, 90.7, 78.5, 31.6, 28.8, 28.7, 28.6, 24.8, 22.6,
20.0, 14.0; HRMS (EI) calcd for C21H25NO 307.1936, found
307.1944.
N-Acetyl-2-(9-tetr a h yd r op yr a n -2-yloxy-3(Z)-n on en -1,5-
d iyn yl)a n ilin e (10f): 1H NMR (CDCl3, 200 MHz) δ 8.53 (d, J
) 8.4 Hz, 1H), 8.22 (s, 1H), 7.55-7.37 (m, 2H), 7.19 (td, J )
7.6, 1.2 Hz, 1H), 6.22-5.18 (m, 2H), 4.66 (s, 1H), 3.98-3.88
(m, 2H), 3.67-3.53 (m, 2H), 3.68 (td, J ) 7.6, 1.8 Hz, 2H), 2.35
(s, 3H), 1.99-1.58 (m, 6H), 0.99-0.93 (m, 2H); 13C NMR
(CDCl3, 50 MHz) δ 168.1, 138.7, 131.6, 129.9, 123.3, 120.8,
119.2, 117.2, 98.8, 94.4, 94.0, 90.8, 78.7, 71.9, 65.7, 62.2, 30.6,
28.9, 25.4, 20.2, 19.5, 16.9; HRMS (EI) calcd for C22H25NO3
351.1834, found 351.1859.
(CDCl3, 50 MHz) δ 156.1, 155.3, 136.1, 132.3, 130.2, 125.7,
122.6, 120.0, 116.5, 113.7, 101.8, 95.7, 89.2, 78.3, 31.1, 28.3,
22.2, 19.9, 13.9; HRMS (EI) calcd for C18H16ONF3 319.1184,
found 319.1161.
N-Tr iflu or oa cet yl-2-(6-p en t yl-3(Z)-h exen -1,5-d iyn yl)-
a n ilin e (10i): 1H NMR (CDCl3, 200 MHz) δ 8.82 (s, 1H), 8.39
(d, J ) 8.0 Hz, 1H), 7.52-7.36 (m, 2H), 7.23 (td, J ) 7.8, 1.2
Hz, 1H), 5.99 (s, 2H), 2.43 (t, J ) 6.6 Hz, 2H), 2.43 (t, J ) 6.6
Hz, 2H), 1.59-1.25 (m, 6H), 0.86 (t, J ) 6.8 Hz, 3H); 13C NMR
(CDCl3, 50 MHz) δ 155.9, 155.1, 136.2, 132.2, 130.1, 125.6,
122.5, 119.8, 116.3, 113.6, 101.2, 95.5, 89.0, 78.1, 31.2, 28.4,
22.3, 19.9, 13.9; HRMS (EI) calcd for C19H18ONF3 333.1341,
found 333.1332.
N-Tr iflu or oa cet yl-2-(6-h exyl-3(Z)-h exen -1,5-d iyn yl)-
a n ilin e (10j): 1H NMR (CDCl3, 200 MHz) δ 8.84 (s, 1H), 8.42
(d, J ) 8.4 Hz, 1H), 7.54-7.38 (m, 2H), 7.25 (td, J ) 7.6, 1.0
Hz, 1H), 6.02 (s, 2H), 2.45 (t, J ) 6.6 Hz, 2H), 1.62-1.21 (m,
8H), 0.89 (t, J ) 6.6 Hz, 3H); 13C NMR (CDCl3, 50 MHz) δ
154.9, 154.1, 135.9, 131.9, 129.9, 125.4, 122.3, 119.6, 116.1,
113.5, 100.9, 95.3, 88.8, 77.9, 31.3, 29.7, 28.5, 22.4, 19.8, 13.9;
HRMS (EI) calcd for C20H22ONF3 347.1497, found 347.1526.
N-Tr iflu or oa cet yl-2-(6-h ep t yl-3(Z)-h exen -1,5-d iyn yl)-
a n ilin e (10k ): 1H NMR (CDCl3, 200 MHz) δ 8.82 (s, 1H), 8.40
(d, J ) 7.2 Hz, 1H), 7.52-7.37 (m, 2H), 7.23 (td, J ) 7.8, 1.4
Hz, 1H), 5.99 (s, 2H), 2.43 (t, J ) 6.6 Hz, 2H), 1.59-1.45 (m,
10H), 0.87 (t, J ) 6.2 Hz, 3H); 13C NMR (CDCl3, 50 MHz) δ
155.9, 155.1, 135.8, 131.9, 129.9, 125.4, 122.3, 119.6, 116.1,
113.5, 100.9, 95.3, 88.9, 77.9, 31.3, 29.7, 28.7, 28.5, 22.4, 19.8,
N-Acetyl-2-(9-tetr a h yd r op yr a n -2-yloxy-3(Z)-d ecen -1,5-
1
d iyn yl)a n ilin e (10g): H NMR (CDCl3, 200 MHz) δ 8.34 (d,
13.9; HRMS (EI) calcd for
361.1645.
C21H22ONF3 361.1654, found
J ) 8.0 Hz, 1H), 8.05 (s, 1H), 7.36-7.21 (m, 2H), 7.01 (t, J )
7.4 Hz, 1H), 5.97-5.84 (m, 2H), 4.46 (s, 1H), 3.76-3.60 (m,
2H), 3.45-3.26 (m, 2H), 2.42 (td, J ) 6.2, 1.4 Hz, 2H), 2.16 (s,
3H), 1.74-1.35 (m, 8H), 0.89-0.77 (m, 2H); 13C NMR (CDCl3,
50 MHz) δ 168.1, 138.8, 131.5, 129.8, 123.2, 120.8, 119.2, 117.0,
99.4, 98.4, 93.9, 90.7, 78.6, 77.6, 77.0, 76.4, 66.7, 62.2, 30.6,
Ack n ow led gm en t. We thank the National Science
Council of the Republic of China for financial support
of this program.
28.8, 25.3, 24.7, 20.9, 19.5, 14.1; HRMS (EI) calcd for C23H27
NO3 365.1991, found 365.2017.
-
Su p p or t in g In for m a t ion Ava ila b le: 1H NMR and 13C
NMR spectra of compounds 1a -g, 2a -g, 9a -g, and 10a -k .
This material is available free of charge via the Internet at
http://pubs.acs.org.
N-Tr iflu or oa cet yl-2-(6-b u t yl-3(Z)-h exen -1,5-d iyn yl)-
a n ilin e (10h ): 1H NMR (CDCl3, 200 MHz) δ 8.81 (s, 1H), 8.38
(d, J ) 8.0 Hz, 1H), 7.50-7.32 (m, 2H), 7.21 (td, J ) 7.6, 1.0
Hz, 1H), 5.97 (s, 2H), 2.41 (t, J ) 6.8 Hz, 2H), 2.41 (t, J ) 6.8
Hz, 2H), 1.57-1.23 (m, 6H), 0.88 (t, J ) 7.0 Hz, 3H); 13C NMR
J O0303158
2110 J . Org. Chem., Vol. 69, No. 6, 2004