Facile stereoselective synthesis of (E)-1-arylseleno-substituted 1,3-enynes and their applications in synthesis of (E)-enediynes

Article abstract of DOI:10.1080/00397910802323064

(E)-1-Iodo-2-arylselenoethylenes 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 to afford (E)-1-arylseleno-substituted 1,3-enynes 3 in high yields. (E)-1-Arylseleno-substituted 1,3-enynes 3 were coupled with alkynylmagnesium bromides 4 in the presence of a catalytic amount of NiCl2(PPh3)2 to give stereoselectively (E)-enediynes 5 in good yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802323064

This article was downloaded by: [Case Western Reserve University]
On: 07 November 2014, At: 06:59
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
Facile Stereoselective
Synthesis of (E)-1-Arylseleno-
Substituted 1,3-Enynes and
Their Applications in Synthesis
of (E)-Enediynes
Xiaoniu Fang a b , Minhua Jiang a , Ronghua Hu b
Mingzhong Cai a
&
a Department of Chemistry , Jiangxi Normal
University , Nanchang, China
b Department of Chemistry , Jinggangshan
University , Jian, China
Published online: 31 Oct 2008.
To cite this article: Xiaoniu Fang , Minhua Jiang , Ronghua Hu & Mingzhong Cai
(2008) Facile Stereoselective Synthesis of (E)-1-Arylseleno-Substituted 1,3-Enynes
and Their Applications in Synthesis of (E)-Enediynes, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:23,
4170-4181, DOI: 10.1080/00397910802323064
To link to this article: http://dx.doi.org/10.1080/00397910802323064
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no

representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Synthetic Communications1, 38: 4170–4181, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802323064
Facile Stereoselective Synthesis of (E)-1-
Arylseleno-Substituted 1,3-Enynes and Their
Applications in Synthesis of (E)-Enediynes
Xiaoniu Fang,1,2 Minhua Jiang,1 Ronghua Hu,2 and Mingzhong Cai1
1Department of Chemistry, Jiangxi Normal University,
Nanchang, China
2Department of Chemistry, Jinggangshan University, Jian, China
Abstract: (E)-1-Iodo-2-arylselenoethylenes 1 underwent the Sonogashira cou-
pling reactions with terminal alkynes 2 to afford (E)-1-arylseleno-substituted
1,3-enynes 3 in high yields. (E)-1-Arylseleno-substituted 1,3-enynes 3 were
coupled with alkynylmagnesium bromides 4 in the presence of a catalytic amount
of NiCl2(PPh3)2 to give stereoselectively (E)-enediynes 5 in good yields.
Keywords: (E)-1-Arylseleno-substituted 1,3-enyne, (E)-enediyne, nickel catalysis,
Sonogashira coupling, stereoselective synthesis
INTRODUCTION
Enyne systems have attracted much attention from synthetic organic che-
mists because enynes show interesting chemical and biological reactiv-
ities.[1] Conjugated enynes are also important synthetic intermediates
because the conjugated enyne moiety can be readily converted in a stereo-
specific manner into the corresponding diene system.[2] Recently, Hara
et al. described the formation of highly substituted enynes using a cou-
pling reaction between alkenylzirconium compounds and alkynyl
halides.[3] Cadierno et al. reported the stereoselective synthesis of chiral
terminal (E)-1,3-enynes derived from the optically active aldehydes.[4]
Received January 13, 2008.
Address correspondence to Mingzhong Cai, Department of Chemistry, Jiangxi
Normal University, Nanchang 330022, China. E-mail: caimzhong@163.com
4170

(E)-1-Arylseleno-Substituted 1,3-Enynes
4171
The stereocontrolled synthesis of 1,3-enynes containing metal or
heteroatom functional groups has also attracted considerable interest in
organic synthesis because many useful functional group transformations
can be achieved by introduction and removal of metal or heteroatom
functions. The stereoselective synthesis of 1,3-enynylsulfides,[5] 1,3-
enynyltellurides,[6]
1,3-enynylsulfones,[7]
1,3-enynylsilanes,[8]
1,3-
enynylstannanes,[9] and fluoro or CF3-substituted 1,3-enynes[10] has
already been described in the literature. The synthesis of (E)-2-arylseleno-
substituted 1,3-enynes has also been reported[11]; however, report on the
synthesis of (E)-1-arylseleno-substituted 1,3-enynes is rare. Sonogashira
coupling is a reliable and convenient reaction for constructing enyne unit
and has often been used for the preparation of such compounds.[12]
Herein, we report that (E)-1-arylseleno-substituted 1,3-enynes could
be conveniently synthesized via Sonogashira coupling reactions of
(E)-1-iodo-2-arylselenoethylenes with terminal alkynes (Scheme 1).
RESULTS AND DISCUSSION
(E)-1-Iodo-2-arylselenoethylenes 1 were easily prepared by the hydrozir-
conation of arylselenoacetylenes, followed by the reaction with iodine
according to a literature procedure.[13] (E)-1-Iodo-2-arylselenoethylenes
1 are difunctional group reagents in which two synthetically versatile
groups are linked to the olefinic carbon atoms and can be considered
both as vinylic selenides and as vinylic iodides. We carried out the
Sonogashira coupling reactions of (E)-1-iodo-2-arylselenoethylenes 1
with terminal alkynes 2; the experimental results are summarized in
Table 1. As shown in Table 1, the Sonogashira coupling reactions
proceeded smoothly in piperidine at room temperature in the presence
of catalytic amounts of Pd(PPh3)4 and CuI to afford stereoselectively
desired (E)-1-arylseleno-substituted 1,3-enynes 3 in high yields. It is well
documented that the Sonogashira coupling reaction of vinylic iodides
with terminal alkynes in the presence of a palladium and CuI cocatalyst
occurs with retention of configuration.[12] The E-configuration of the
Scheme 1. Synthesis of (E)-1-arylseleno-substituted 1,3-enynes.

4172
X. Fang et al.
Table 1. Synthesis of (E)-1-arylseleno-substituted 1,3-enynes 3a–ga
Entry
Ar
R
Product
Yieldb (%)
1
2
3
4
5
6
7
Ph
Ph
Ph
Ph
Ph
n-C4H9
n-C6H13
Me3Si
MeOCH2
Ph
3a
3b
3c
3d
3e
3f
88
87
85
90
89
86
88
4-ClC6H4
4-MeC6H4
Me3Si
Me3Si
3g
aThe reactions were performed with 1.0 mmol of 1, 1.5 mmol of 2, 0.05 mmol of
Pd(PPh3)4, and 0.1 mmol of CuI in 3 mL of piperidine at room temperature.
bIsolated yield based on 1 used.
compounds 3a–g has been proved by their 1H NMR spectra, which show
a doublet at d ¼ 5.64–5.80 with a coupling constant of 15.6–16.0 Hz.
Enediyne compounds have recently received considerable attention
because they can be used not only to study on the mechanism for their
function in antitumor antibiotics[14–16] such as dynemicin, neocarzinosta-
tin, and esperamicin but also are utilized in syntheses of oligoenynes and
oligoenediynes as well as p-conjugated polymers for electronic and
photonic applications.[17] Very recently, they have been widely used as
important synthetic intermediates in organic synthesis.[18] It is well
known that vinylic selenides can couple with Grignard reagents in the
presence of a catalytic amount of nickel-phosphine complexes to afford
the corresponding unsaturated hydrocarbons with loss of selenium-
containing groups.[19] We carried out the cross-coupling reactions of
(E)-1-arylseleno-substituted 1,3-enynes 3 with alkynylmagnesium bro-
mides 4 in ether in the presence of a catalytic amount of NiCl2(PPh3)2
to afford the selenium-free (E)-enediynes 5 (Scheme 2). The typical
results are summarized in Table 2. As shown in Table 2, the cross-
coupling reactions of (E)-1-arylseleno-substituted 1,3-enynes 3 with
alkynylmagnesium bromides
4 proceeded smoothly under mild
Scheme 2. Synthesis of (E)-enediynes.

(E)-1-Arylseleno-Substituted 1,3-Enynes
Table 2. Synthesis of (E)-enediynes 5a–ea
4173
Entry
Ar
R
R1
Product
Yieldb (%)
1
2
3
4
5
Ph
Ph
4-MeC6H4
4-MeC6H4
Ph
n-C4H9
n-C6H13
Me3Si
Me3Si
Ph
Me3Si
n-C4H9
Me3Si
n-C6H13
n-C6H13
5a
5b
5c
5d
5e
72
75
81
76
69
aThe reactions were performed with 1.0 mmol of 3, 2.5 mmol of 4, and
0.03 mmol of NiCl2(PPh3)2 in 12 mL of Et2O at reflux temperature.
bIsolated yield based on 3 used.
conditions to give the corresponding (E)-enediynes 5 in good yields. The
E-configuration of the compounds 5a, 5d, and 5e has been proved by
1
their H NMR spectra, which show two doublets at d ¼ 5.88–6.12 with
a
coupling constant of 16.0 Hz. Because arylseleno-substituted
compounds are toxic and give off a bad smell, we tried to combine the
Sonogashira coupling and Ni-catalyzed coupling reactions into a one-
pot reaction to synthesize (E)-enediynes 5, but this was unsuccessful.
EXPERIMENTAL
General
IR spectra were obtained on a Perkin-Elmer 683 instrument as neat films.
1H NMR spectra were recorded on a Bruker AC-400 (400-MHz) spectro-
meter with TMS as an internal standard using CDCl3 as solvent. 13C
NMR spectra were recorded on a Bruker AC-400 (100-MHz) spectro-
meter using CDCl3 as solvent. Mass spectra were determined on a
Finnigan 8230 mass spectrometer. Microanalyses were measured using
a Yanaco MT-3 CHN microelemental analyzer. Piperidine was dried
over potassium hydroxide (KOH) and distilled before use. Diethyl ether
was distilled from sodium benzophenone ketyl prior to use.
General Procedure for the Synthesis of (E)-1-Arylseleno-Substituted
1,3-Enynes 3a–g
(E)-1-Iodo-2-arylselenoethylene 1 (1.0 mmol), Pd(PPh3)4 (0.05 mmol),
piperidine (3 mL), and CuI (0.1 mmol) were added to a flask under argon,

4174
X. Fang et al.
and the resulting mixture was stirred at room temperature for 5 min.
Terminal alkyne 2 (1.5 mmol) was added to this solution, and the reaction
mixture was stirred at room temperature for 3 h, quenched with
sat. NH4Cl aq. solution (10 mL) at 0 ꢀC, and extracted with Et2O
(2 ꢁ 25 mL). The ethereal solution was washed with water (2 ꢁ 10 mL)
and dried over MgSO4. The solvent was removed under vacuum, and
the residue was purified by flash chromatography on silica gel eluting
with light petroleum ether (bp 30–60 ꢀC).
Data
(E)-1-Phenylseleno-1-octen-3-yne (3a)
Oil, bp 78 ꢀC (0.35 torr). IR (film): n (cmꢂ1) 3058, 2957, 2931, 2871, 2212,
1708, 1578, 1477, 930, 736, 690; 1H NMR (CDCl3): d 7.52–7.50 (m, 2H),
7.32–7.30 (m, 3H), 6.99 (d, J ¼ 15.6 Hz, 1H), 5.80 (d, J ¼ 15.6 Hz, 1H),
2.31–2.26 (m, 2H), 1.52–1.37 (m, 4H), 0.91 (t, J ¼ 7.2 Hz, 3H); 13C
NMR (CDCl3): d 133.3, 131.8, 129.4, 128.8, 127.9, 114.0, 91.6, 78.9,
30.7, 22.0, 19.2, 13.6; MS (EI): m=z 264 (Mþ, 17), 263 (54), 142 (100),
129 (56), 115 (70), 91 (63), 77 (74). Anal. calc. for C14H16Se: C, 63.88;
H, 6.13. Found: C, 63.59; H, 6.16%.
(E)-1-Phenylseleno-1-decen-3-yne (3b)
Oil, bp 82 ꢀC (0.3 torr). IR (film): n (cmꢂ1) 3059, 2955, 2930, 2857, 2211,
1712, 1578, 1477, 930, 736, 690; 1H NMR (CDCl3): d 7.52–7.50 (m, 2H),
7.32–7.30 (m, 3H), 6.99 (d, J ¼ 16.0 Hz, 1H), 5.80 (d, J ¼ 16.0 Hz, 1H),
2.30–2.25 (m, 2H), 1.53–1.47 (m, 2H), 1.39–1.25 (m, 6H), 0.88 (t,
J ¼ 6.8 Hz, 3H); 13C NMR (CDCl3): d 133.3, 131.8, 129.4, 128.8, 127.8,
114.0, 91.7, 78.9, 31.3, 28.6, 28.5, 22.5, 19.5, 14.1; MS (EI): m=z 292
(Mþ, 13), 291 (51), 142 (100), 129 (57), 115 (75), 91 (85), 77 (84). Anal.
calc. for C16H20Se: C, 65.97; H, 6.92. Found: C, 65.74; H, 6.78%.
(E)-1-Phenylseleno-4-(trimethylsilyl)-1-buten-3-yne (3c)
Oil, bp 89 ꢀC (0.5 torr). IR (film): n (cmꢂ1) 3059, 2958, 2142, 1712, 1578,
1250, 844, 690; 1H NMR (CDCl3): d 7.54–7.52 (m, 2H), 7.34–7.32 (m, 3H),
7.21 (d, J ¼ 16.0 Hz, 1H), 5.71 (d, J ¼ 16.0 Hz, 1H), 0.16 (s, 9H); 13C NMR
(CDCl3): d 136.4, 134.1, 129.6, 128.3, 127.8, 111.7, 103.3, 95.2, ꢂ0.12; MS
(EI): m=z 280 (Mþ, 5.8), 250 (55), 78 (44), 73 (100). Anal. calc. for C13 H16
SiSe: C, 55.90; H, 5.77. Found: C, 55.62; H, 5.79%.

(E)-1-Arylseleno-Substituted 1,3-Enynes
4175
(E)-1-Phenylseleno-5-methoxy-1-penten-3-yne (3d)
Oil, bp 73 ꢀC (0.4 torr). IR (film): n (cmꢂ1) 3057, 2929, 2204, 1713,
1578, 1094, 930, 739, 690; 1H NMR (CDCl3): d 7.55–7.51 (m, 2H),
7.35–7.32 (m, 3H), 7.16 (d, J ¼ 15.6 Hz, 1H), 5.76 (d, J ¼ 15.6 Hz, 1H),
4.18 (s, 2H), 3.37 (s, 3H); 13C NMR (CDCl3): d 135.3, 133.8, 129.6,
128.2, 128.1, 111.5, 85.7, 84.7, 60.4, 57.6; MS (EI): m=z 252 (Mþ, 16),
251 (57), 220 (78), 142 (93), 129 (82), 115 (72), 95 (100), 77 (84), 51
(77). Anal. Calc. for C12H12OSe: C, 57.38; H, 4.81. Found: C, 57.19;
H, 4.56%.
(E)-1-Phenylseleno-4-phenyl-1-buten-3-yne (3e)
Oil, bp 118 ꢀC (0.6 torr). IR (film): n (cmꢂ1) 3057, 2196, 1706, 1597,
1
1565, 1488, 928, 688; H NMR (CDCl3): d 7.58–7.21 (m, 11H), 5.71
(d, J ¼ 15.6 Hz, 1H); 13C NMR (CDCl3): d 134.6, 133.8, 131.6,
131.4, 129.6, 128.4, 128.3, 128.2, 128.1, 112.2, 90.2, 87.9; MS (EI):
m=z 284 (Mþ, 74), 228 (82), 204 (78), 169 (100), 126 (66), 77 (44).
Anal. calc. for C16H12Se: C, 67.85; H, 4.27. Found: C, 67.59; H,
4.08%.
(E)-1-[(4-Chlorophenyl)seleno]-4-(trimethylsilyl)-1-buten-3-yne (3f)
Oil, bp 85 ꢀC (0.35 torr). IR (film): n (cmꢂ1) 2958, 2110, 1556, 1473, 1254,
1089, 930, 842, 760; 1H NMR (CDCl3): d 7.45 (d, J ¼ 8.4 Hz, 2H), 7.29 (d,
J ¼ 8.4 Hz, 2H), 7.14 (d, J ¼ 15.6 Hz, 1H), 5.73 (d, J ¼ 15.6 Hz, 1H), 0.17
(s, 9H); 13C NMR (CDCl3): d 135.5, 135.4, 134.9, 130.0, 126.2, 112.6,
103.1, 95.8, 0.01; MS (EI): m=z 316 (Mþ, 37Cl, 15), 314 (Mþ, 35Cl, 31),
191 (100), 189 (53), 156 (47), 73 (36). Anal. calc. for C13H15ClSiSe: C,
49.76; H, 4.82. Found: C, 49.54; H, 4.89%.
(E)-1-[(4-Methylphenyl)seleno]-4-(trimethylsilyl)-1-buten-3-yne (3g)
Oil, bp 82 ꢀC (0.4 torr). IR (film): n (cmꢂ1) 2960, 2163, 1563, 1489, 1251,
927, 843, 803, 760; 1H NMR (CDCl3): d 7.42 (d, J ¼ 8.4 Hz, 2H), 7.19 (d,
J ¼ 15.6 Hz, 1H), 7.13 (d, J ¼ 8.4 Hz, 2H), 5.64 (d, J ¼ 15.6 Hz, 1H), 2.34
(s, 3H), 0.16 (s, 9H); 13C NMR (CDCl3): d 138.8, 137.1, 134.7, 130.5,
123.9, 111.1, 103.6, 95.1, 21.3, 0.04; MS (EI): m=z 294 (Mþ, 14), 263
(35), 91 (43), 73 (100). Anal. calc. for C14H18SiSe: C, 57.32; H, 6.18.
Found: C, 57.50; H, 6.31%.

4176
X. Fang et al.
General Procedure for the Synthesis of (E)-Enediynes 5a–e
To a mixture of (E)-1-arylseleno-substituted 1,3-enyne 3 (1.0 mmol) and
NiCl2(PPh3)2 (0.03 mmol) in diethyl ether (8 mL), alkynylmagnesium bro-
mide 4 (2.5 mmol) in diethyl ether (4 mL) was added under argon at room
temperature with stirring. The resulting mixture was heated to reflux for
10 h. The mixture was treated with sat. NH4Cl aq. solution (15 mL) at
0 ꢀC and extracted with diethyl ether (2 ꢁ 20 mL). The ethereal solution
was washed with water (2 ꢁ 20 mL) and dried (MgSO4). Removal of
the solvent under reduced pressure gave an oil, which was purified by pre-
parative thin-layer chromatography (TLC) on silica gel eluting with light
petroleum ether (bp 30–60 ꢀC).
Data
(E)-1-(Trimethylsilyl)-6-butyl-3-hexen-1,5-diyne (5a)
Oil, bp 65 ꢀC (0.6 torr). IR (film): n (cmꢂ1) 3033, 2960, 2162, 2118, 1250,
1073, 937, 844; 1H NMR (CDCl3): d 6.02 (d, J ¼ 16.0 Hz, 1H), 5.89
(d, J ¼ 16.0 Hz, 1H), 2.36–2.31 (m, 2H), 1.54–1.37 (m, 4H), 0.92
(t, J ¼ 7.2 Hz, 3H), 0.20 (s, 9H); 13C NMR (CDCl3): d 122.8, 119.3,
103.4, 98.9, 96.8, 79.0, 30.6, 22.0, 19.4, 13.6, ꢂ0.17; MS (EI): m=z 204
(Mþ, 9.4), 190 (100), 73 (68). Anal. calc. for C13H20Si: C, 76.39; H,
9.86. Found: C, 76.25; H, 9.69%.
(E)-1-Hexyl-6-butyl-3-hexen-1,5-diyne (5b)
Oil, bp 58 ꢀC (0.45 torr). IR (film): n (cmꢂ1) 3031, 2960, 2163, 2118, 1252,
1
1073, 935, 844; H NMR (CDCl3): d 5.88 (s, 2H), 2.34–2.29 (m, 4H),
1.55–1.24 (m, 12H), 0.93–0.87 (m, 6H); 13C NMR (CDCl3): d 120.3,
120.2, 95.0, 94.9, 79.1, 31.3, 30.7, 28.6, 22.5, 22.0, 19.6, 19.3, 14.0, 13.6;
MS (EI): m=z 216 (Mþ, 4.5), 146 (52), 132 (95), 118 (98), 115 (80), 91
(100). Anal. calc. for C16H24: C, 88.82; H, 11.18. Found: C, 88.55; H,
11.27%.
(E)-1,6-Bis(trimethylsilyl)-3-hexen-1,5-diyne (5c)
White solid, mp 71–72 ꢀC (lit.[20] mp 72 ꢀC). IR (film): n (cmꢂ1) 2955,
1
2174, 2127, 1251, 1093, 933, 843; H NMR (CDCl3): d 6.01 (s, 2H),

(E)-1-Arylseleno-Substituted 1,3-Enynes
4177
0.20 (s, 9H); 13C NMR (CDCl3): d 121.7, 102.9, 100.7, ꢂ0.24; MS
(EI): m=z 220 (Mþ, 11), 207 (75), 205 (69), 191 (43), 155 (38), 73
(100). Anal. calc. for C12H20Si2: C, 65.37; H, 9.14. Found: C, 65.56; H,
9.27%.
(E)-1-(Trimethylsilyl)-6-hexyl-3-hexen-1,5-diyne (5d)
Oil, bp 71 ꢀC (0.5 torr). IR (film): n (cmꢂ1) 3033, 2959, 2162, 2118, 1250,
1
1073, 937, 844; H NMR (CDCl3): d 6.01 (d, J ¼ 16.0 Hz, 1H), 5.88 (d,
J ¼ 16.0 Hz, 1H), 2.35–2.30 (m, 2H), 1.54–1.26 (m, 8H), 0.89 (t,
J ¼ 7.2 Hz, 3H), 0.19 (s, 9H); 13C NMR (CDCl3): d 122.8, 119.3, 103.4,
98.9, 96.8, 79.0, 31.3, 28.6, 28.5, 22.5, 19.7, 14.0, ꢂ 0.18; MS (EI): m=z
232 (Mþ, 8.5), 217 (35), 73 (100). Anal. calc. for C15 H24 Si: C, 77.51;
H, 10.41. Found: C, 77.27; H, 10.20%.
(E)-1-Hexyl-6-phenyl-3-hexen-1,5-diyne (5e)
Oil, bp 68 ꢀC (0.35 torr). IR (film): n (cmꢂ1) 3032, 2927, 2856, 2214, 1261,
1
1023, 934, 754; H NMR (CDCl3): d 7.46–7.41 (m, 2H), 7.38–7.33 (m,
3H), 6.12 (d, J ¼ 16.0 Hz, 1H), 6.06 (d, J ¼ 16.0 Hz, 1H), 2.38–2.33 (m,
2H), 1.56–1.25 (m, 8H), 0.90 (t, J ¼ 7.2 Hz, 3H); 13C NMR (CDCl3): d
132.5, 131.5, 129.2, 128.4, 121.7, 119.4, 96.6, 93.4, 88.1, 79.2, 31.3,
29.7, 28.5, 22.5, 19.7, 14.1; MS (EI): m=z 236 (Mþ, 34), 202 (100), 178
(33), 165 (45). Anal. calc. for C18H20: C, 91.47; H, 8.53. Found: C,
91.18; H, 8.29%.
CONCLUSION
In conclusion, we have developed an efficient and stereoselective method
for the synthesis of (E)-1-arylseleno-substituted 1,3-enynes and (E)-
enediynes. The present method has the advantages of readily available
starting materials, straightforward and simple procedures, mild reaction
conditions, and good yields.
ACKNOWLEDGMENT
We thank the Natural Science Foundation of Jiangxi Province in China
(2007GZW0172) for financial support.

4178
X. Fang et al.
REFERENCES
1. (a) Kouno, R.; Okauchi, T.; Nakamura, M.; Ichikawa, J.; Minami, T. Synth-
esis and synthetic utilization of a-functionalized vinylphosphonates bearing
b-oxy or b-thio substituents. J. Org. Chem. 1998, 63, 6239–6246; (b) Ikeda,
S.; Sato, Y. Synthesis of stereodefined enynes by the nickel-catalyzed cou-
pling reaction of alkynyltins, alkynes and enones. J. Am. Chem. Soc. 1994,
116, 5975–5976; (c) Stefani, H. A.; Cella, R.; Dorr, F. A.; Pereira, C. M. P.;
Zeni, G.; Gomes, M. Synthesis of 1,3-enynes via Suzuki-type reaction of
vinylic tellurides and potassium alkynyltrifluoroborate salts. Tetrahedron
Lett. 2005, 46, 563–567.
2. (a)Magriotis, P. A.; Kim, K. D. Ireland–Claisen rearrangements of enediyne
lactones: Tandem Claisen–Bergman strategy for stereocontrolled tetrahydro-
naphthalene synthesis. J. Am. Chem. Soc. 1993, 115, 2972–2973; (b) Miller,
J. A.; Zweifel, G. Hydroalumination of 1-(trimethylsilyl)-1,3-diynes: Synth-
esis of stereodefined enynes and dienes. J. Am. Chem. Soc. 1983, 105,
1383–1384; (c) Corey, E. J.; Tramontano, A. Total synthesis of bongkrekic
acid. J. Am. Chem. Soc. 1984, 106, 462–463; (d) Karatholuvhu, M. S.; Fuchs,
P. L. 3,3,3-Trichloropropyl-1-triphenylphosphorane: A reagent for the synth-
esis of (Z)-1,3-enynes, (Z,Z)-1-chloro-1,3-dienes, and 1,3-diynes. J. Am.
Chem. Soc. 2004, 126, 14314–14315; (e) Yoshida, M.; Ohsawa, Y.; Ihara,
M. Palladium-catalyzed carbon dioxide elimination–fixation reaction of 6-
methoxycarbonyloxy-2,4-hexadien-1-ols. Tetrahedron 2006, 62, 11218–11226.
3. Hara, R.; Liu, Y.; Sun, W.-H.; Takahashi, T. Highly substituted enyne for-
mation by coupling reaction of alkenylzirconium compounds with alkynyl
halides. Tetrahedron Lett. 1997, 38, 4103–4106.
4. Cadierno, V.; Gamasa, M. P.; Gimeno, J. Stereoselective synthesis of
chiral terminal (E)-1,3-enynes derived from the aldehydes (1 R)-(ꢂ)-myrtenal
and (S)-(ꢂ)-perillaldehyde using the alkynyl-phosphonio complex
[Ru{C ꢃ CCH2(PPh3)}(g5-C9H7) (PPh3)2][PF6] as synthon. J. Organomet.
Chem. 2001, 621, 39–45.
5. (a) Koreeda, M.; Yang, W. The chemistry of 1,2-dithiins: Synthesis of 1,2-
dithiin and 3,6-disubstituted 1,2-dithiins. Synlett 1994, 201–203; (b) Cai,
M.; Wang, D.; Wang, P. Novel stereoselective synthesis of (Z)-2-arylthio-
substituted 1,3-enynes from (E)-a-stannylvinyl sulfides and 1-alkynes.
J. Chem. Res. 2006, 504–506.
6. (a) Huang, X.; Wang, Y. P. Stereoselective synthesis of (Z)- or (E)-b-
bromovinyl tellurides and their application in the synthesis of trisubstituted
alkenes. Tetrahedron Lett. 1996, 37, 7417–7420; (b) Cai, M.; Chen, J. Stereo-
selective synthesis of 1,3-enynyltellurides via palladium catalyzed cross cou-
pling reaction of (E)-a-iodovinyltellurides. J. Chem. Res. 2004, 840–842.
7. (a) Trost, B. M.; Chan, C.; Ruhter, G. Metal-mediated approach to enynes.
J. Am. Chem. Soc. 1987, 109, 3486–3487; (b) Trost, B. M.; Sorum, M. T.;
Chan, C.; Harms, A. E.; Ruhter, G. Palladium-catalyzed additions of term-
inal alkynes to acceptor alkynes. J. Am. Chem. Soc. 1997, 119, 698–708. (c)
Ye, F.; Orita, A.; Doumoto, A.; Otera, J. Double elimination protocol
for access to unsymmetrically substituted aromatic polyynes starting from

(E)-1-Arylseleno-Substituted 1,3-Enynes
4179
sulfones and aldehydes. Tetrahedron 2003, 59, 5635–5643; (d) Yoshimatsu,
M.; Gotoh, S.; Gotoh, E.; Tanabe, G.; Muraoka, O. Convenient synthesis
of 2-alkynyl-cyclopropanes and -oxiranes. J. Chem. Soc., Perkin Trans. 1
1997, 3035–3041.
8. (a) Chatani, N.; Amishiro, N.; Murai, S. A new catalytic reaction involving
oxidative addition of iodotrimethylsilane to palladium(0): Synthesis of stereo-
defined enynes by the coupling of Me3SiI, acetylenes, and acetylenic tin
reagents. J. Am. Chem. Soc. 1991, 113, 7778–7780; (b) Cai, M.; Hao, W.; Zhao,
H.; Song, C. Stereoselective synthesis of 1,3-enynylsilanes via hydromag-
nesiation reaction of alkynylsilanes. J. Chem. Res. 2003, 485–486.
9. (a) Huang, X.; Zhong, P. A facile regio- and stereocontrolled synthesis of (Z)-
1-en-3-yn-2-ylstannanes via a alkynyliodonium tosylates coupling with gem-
stannyl zirconocene alkenes. J. Chem. Soc., Perkin Trans. 1 1999, 1543–1545;
(b) Cai, M.; Zhao, H.; Ye, H.; Xia, J.; Song, C. Stereoselective synthesis
of 1,3-enynylstannanes via palladium catalyzed cross-coupling reaction of
(E)-a-iodovinylstannanes. J. Chem. Res. 2003, 344–346.
10. (a) Yoshida, M.; Yoshikawa, S.; Fukuhara, T.; Yoneda, N.; Hara, S.
Stereoselective synthesis of (E)-1-fluoro-1,3-enynes. Tetrahedron 2001, 57,
7143–7148; (b) Legros, J.; Crousse, B.; Bonnet-Delpon, D.; Begue, J. P.
Palladium-catalyzed reaction of functionalized b-trifluoromethyl vinyl
bromides with terminal alkynes and alkenes. J. Fluor. Chem. 2001, 107,
121–125; (c) Shen, Y.; Wang, G.; Sun, J. Stereocontrolled synthesis of tri-
fluoromethylated (E)- or (Z)-ynenyl sulfones via sequential transformations.
J. Chem. Soc., Perkin Trans. 1 2001, 519–522.
11. (a) Braga, A. L.; Zeni, G.; Andrade, L. H.; Silveira, C. C.; Stefani, H. A.
Stereospecific formation of chalcogenoenynes via palladium catalyzed
cross-coupling reaction of a-bromovinylic chalcogenides. Synthesis 1998,
39–41; (b) Ma, Y.; Huang, X. A novel synthesis of 1,3-enynylselenides via
cross coupling of (E)-a-selanylvinylstannanes with haloalkynes. Synth. Com-
mun. 1997, 27, 3441–3447; (c) Cai, M. Z.; Peng, C. Y.; Zhao, H.; Huang, J. D.
Stereoselective synthesis of 1,3-enynylselenides via palladium catalyzed cross
coupling reaction. J. Chem. Res. 2002, 376–377; (d) Zhong, P.; Huang, N. A
facile regio- and stereocontrolled synthesis of (Z)-1,3-enynyl selenides via
cross coupling of (E)-a-iodovinyl selenides with terminal alkynes. Synth.
Commun. 2002, 32, 139–145.
12. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. A convenient synthesis of acet-
ylenes: Catalytic substitutions of acetylenic hydrogen with bromoalkenes,
iodoarenes and bromopyridines. Tetrahedron Lett. 1975, 4467–4470; (b)
Alami, M.; Linstrumelle, G. An efficient palladium-catalyzed reaction
of vinyl chlorides with terminal acetylenes. Tetrahedron Lett. 1991, 32,
6109–6112.
13. Zhu, L.-S.; Huang, Z.-Z.; Huang, X. Stereoselective synthesis of (E)-
1-halo-2-arylselenoethylenes via hydrozirconation of arylselenoethyne. J.
Chem. Res. 1996, 112–113.
14. (a) Myers, A. G.; Gragovich, P. S. Design and synthesis of a system for ene-
diyne formation by anthraquinone reductive activation. J. Am. Chem. Soc.

4180
X. Fang et al.
1992, 114, 5859–5860; (b) Wender, P. A.; Zercher, C. K.; Backham, S.;
Haubold, E. M. A photochemically triggered DNA cleaving agent: Synthesis,
mechanistic and DNA cleavage studies on a new analog of the anti-tumor
antibiotic dynemicin. J. Org. Chem. 1993, 58, 5867–5869; (c) Iida, K.;
Hirama, M. Synthesis and characterization of nine-membered cyclic ene-
diynes, models of the C-1027 and kedarcidin chromophores: Equilibration
with a p-benzyne biradical and kinetic stabilization. J. Am. Chem. Soc.
1995, 117, 8875–8876.
15. (a) Oku, N.; Matsunaga, S.; Fusetani, N. Shishijimicins A-C, novel enediyne
antitumor antibiotics from the ascidian Ddemum proli ferum. J. Am. Chem.
Soc. 2003, 125, 2044–2045; (b) Kennedy, D. R.; Beermann, T. A. The radio-
mimetic enedyne C-1027 induces unusual DNA damage responses to double-
strand breaks. Biochemistry 2006, 45, 3747–3754; (c) Tachi, Y.; Dai, W. M.;
Tanabe, K.; Nishimoto, S. Synthesis and DNA cleavage reaction character-
istics of enediyne prodrugs activated via an allylic rearrangement by base
or UV irradiation. Bioorg. Med. Chem. 2006, 14, 3199–3209.
16. (a) Inoue, M.; Usuki, T.; Lee, N.; Hirama, M.; Tanaka, T.; Hosoi, F.; Ohie,
S.; Otani, T. Antitumor enediyne chromoprotein C-1027: Mechanistic inves-
tigation of the chromophore-mediated self-decomposition pathway. J. Am.
Chem. Soc. 2006, 128, 7896–7903; (b) Christianson, C. V.; Montavon, T. J.;
Van Lanen, S. G.; Shen, B.; Bruner, S. D. The structure of L-tyrosine 2,3-
aminomutase from the C-1027 enediyne antitumor antibiotic biosynthetic
pathway. Biochemistry 2007, 46, 7205–7214.
17. (a) Tour, J. M. Conjugated macromolecules of precise length and constitu-
tion. Organic synthesis for the construction of nanoarchitectures. Chem.
Rev. 1996, 96, 537–554; (b) Kraft, A.; Grimsdale, A. C.; Holmes, A. C.
Electro-luminescent conjugated polymers-seeing polymers in a new light.
Angew. Chem., Int. Ed. 1998, 37, 402–428; (c) Martin, R. E.; Diederich, F.
Linear monodisperse p-conjugated oligomers: Model compounds for poly-
mers and more. Angew. Chem., Int. Ed. 1999, 38, 1350–1377; (d) Pron, A.;
Rannou, P. Processible conjugated polymers: From organic semiconductors
to organic metals and superconductors. Prog. Polym. Sci. 2002, 27, 135–190.
18. (a) O’Connor, J. M.; Friese, S. J.; Rodgers, B. L. A transition-metal-catalyzed
enediyne cycloaromatization. J. Am. Chem. Soc. 2005, 127, 16342–16343; (b)
Poloukhtine, A.; Popik, V. V. Two-photon photochemical generation of reac-
tive enediyne. J. Org. Chem. 2006, 71, 7417–7421; (c) Usuki, T.; Nakanishi,
K.; Ellestad, G. A. Spin-trapping of the p-benzyne intermediates from
ten-membered enediyne calicheamicin. Org. Lett. 2006, 8, 5461–5463; (d)
Brzostowska, E. M.; Hoffmann, R.; Darish, C. A. Tuning the Bergman
cyclization by introduction of metal fragments at various positions of
the enediyne. Metalla-Bergman cyclizations. J. Am. Chem. Soc. 2007, 129,
4401–4409; (e) Perrin, C. L.; Rodgers, B. L.; O’Connor, J. M. Nucleophilic
addition to a p-benzyne derived from an enediyne: A new mechanism for halide
incorporation into biomolecules. J. Am. Chem. Soc. 2007, 129, 4795–4799.
19. (a) Okamura, H.; Miura, M.; Kosugi, K.; Takei, H. Cross-coupling
of alkenyl, aryl or allylic selenides and Grignard reagents catalyzed by

(E)-1-Arylseleno-Substituted 1,3-Enynes
4181
nickel-phosphine complexes. Tetrahedron Lett. 1980, 21, 87–90; (b) Hevesi,
L.; Hermans, B.; Allard, C. Nickel and palladium catalyzed coupling of vinyl
selenides with trimethylsilylmethylmagnesium chloride: A new synthesis of
allyl silanes. Tetrahedron Lett. 1994, 35, 6729–6730; (c) Zhu, L.-S.; Huang,
Z.-Z.; Huang, X. Stereoselective synthesis of (E,E)-1-arylselenobutadienes
by cross-coupling reactions in the presence of palladium catalyst. Tetrahedron
1996, 52, 9819–9822.
20. Walker, J. A.; Bitler, S. P.; Wudl, F. 1,6-Bis(trimethylsilyl)hexa-1,5-diyn-
3-ene: Models to determine the structure of polydiacetylenes. J. Org. Chem.
1984, 49, 4733–4734.