Synthesis of tetrasubstituted olefins by stereoselective allylzincation- Negishi tandem reaction of acetylenic sulfones

Article abstract of DOI:10.3184/030823408X338729

Tetrasubstituted olefins containing a 1,3,6-triene structural unit can be regio- and stereoselectively synthesised in good yields under mild conditions in one pot, by allylzincation-Negishi tandem reaction of acetylenic sulfones with allylzinc bromide and alkenyl halides.

Full text of DOI:10.3184/030823408X338729

JOURNAL OF CHEMICAL RESEARCH 2008
AUGUST, 429–431
RESEARCH PAPER 429
Synthesis of tetrasubstituted olefins by stereoselective allylzincation–
Negishi tandem reaction of acetylenic sulfones
Jianying Li,a,b Shengyong Youa and Mingzhong Caia*
aDepartment of Chemistry, Jiangxi Normal University, Nanchang, Jiangxi 330022, P.R. China
bDepartment of Chemistry, Jingdezhen Comprehensive College, Jingdezhen, Jiangxi 333000, P.R. China
Tetrasubstituted olefins containing a 1,3,6-triene structural unit can be regio- and stereoselectively synthesised in
good yields under mild conditions in one pot, by allylzincation–Negishi tandem reaction of acetylenic sulfones with
allylzinc bromide and alkenyl halides.
Keywords: DFHW\OHQLFꢀVXOIRQHꢁꢀDOO\O]LQFDWLRQꢁꢀ1HJLVKLꢀFRXSOLQJꢁꢀWDQGHPꢀUHDFWLRQꢁꢀWHWUDVXEVWLWXWHGꢀROH¿QꢁꢀVWHUHRVHOHFWLYHꢀV\QWKHVLV
The stereoselective synthesis of polysubstituted alkenes
remains a challenging problem in organic synthesis and
is still being actively explored because many biologically
active compounds have the structural unit of polysubstituted
alkenes.1-6 Vinyl sulfones are important synthetic
intermediates since the sulfone group both activates the
adjacent multiple carbon-carbon bonds and provides a
useful functional group for further transformation by various
desulfonylation methods.7,8 A variety of methods have been
developed for their preparation including those involving
Horner–Emmons reactions of carbonyl compounds and
sulfonyl phosphoranes,9 Peterson reactions,10ꢀ ȕꢂHOLPLQDWLRQꢀ
of selenosulfones11 and selenosulfonation of acetylene.12
Considering the importance of vinyl sulfones, it is still of
interest to develop new routes of synthesis. Carbometallation
of alkynes by organometallic reagents has been studied
extensively in the synthesis of substituted alkenes.13 Huang14
and Xie15 reported that polysubstituted vinyl sulfones could
be synthesised by carbomagnesiation of acetylenic sulfones.
Organozinc reagents are very important reagents in organic
synthesis due to their high functional group compatibility
and their high reactivity in the presence of a palladium or
nickel catalyst.16-19 However, the synthesis of vinyl sulfones
by the carbozincation reaction of acetylenic sulfones has
received less attention.20 Here we report that tetrasubstituted
ROH¿QVꢀFRQWDLQLQJꢀDꢀꢃꢁꢄꢁꢅꢂWULHQHꢀVWUXFWXUDOꢀXQLWꢀFDQꢀEHꢀUHJLRꢂꢀ
and stereoselectively synthesised in good yields under
mild conditions, in one pot, by allylzincation of acetylenic
sulfones, followed by palladium-catalysed Negishi coupling
with alkenyl halides.
Although reports on the carbozincation of alkynes are
well-known, trapping of the vinyl zinc intermediates formed
by carbozincation of alkynes with an electrophile other than
a proton is rare.16,20 Acetylenic sulfones 1 were prepared
according to a literature procedure.21 It is well known that
the allylzincation of acetylenic sulfones 1 with allylzinc
bromide in THF proceeds highly regio- and stereoselectively
WRꢀJHQHUDWHꢀĮꢂDU\OVXOIRQ\OꢀYLQ\Oꢀ]LQFꢀUHDJHQWVꢀ2; the addition
of allylzinc bromide to acetylenic sulfones is in the pure
syn-fashion.20 To extend the application of the allylzincation
reaction of acetylenic sulfones, considering the fact that
DONHQ\Oꢀ KDOLGHVꢀ DUHꢀ HI¿FLHQWꢀ HOHFWURSKLOHVꢀ DQGꢀ FDQꢀ XQGHUJRꢀ
cross-coupling reaction with organometallic reagents in the
presence of transition metal catalysts, we investigated the
palladium-catalysed Negishi coupling reaction of alkenyl
KDOLGHVꢀZLWKꢀĮꢂDU\OVXOIRQ\OꢀYLQ\Oꢀ]LQFꢀUHDJHQWVꢀ2 obtained by
allylzincation of acetylenic sulfones.
Table 1 The screening of catalysts for the Negishi coupling
of D-arylsulfonyl vinyl zinc reagent 2 (R = n–C4H9) with (E)-1-
iodo-1-hexenea
Entry
Catalyst
Yieldb(%) of 4a
1
2
3
4
5
6
7
Pd(OAc)2 (5 mol%)
PdCl2 (5 mol%)
Pd(PPh3)2Cl2 (5 mol%)
Pd(PPh3)4 (2 mol%)
Pd(PPh3)4 (5 mol%)
Pd(PPh3)4 (10 mol%)
Ni(PPh3)2Cl2 (5 mol%)
0
0
38
65
83
85
0
aThe Negishi reaction was performed with 1.0 mmol of 2 and
1.0 mmol of (E)-1-iodohex-1-ene at 25°C for 12 h.
bIsolated yield based on 1 used.
and PdCl2 were ineffective for this coupling reaction (entries
1 and 2). Ni(II) catalysts such as Ni(PPh3)2Cl2 showed no
catalytic activity (entry 7). (E)-1-Phenylsulfonyl-2-butylpenta-
1,4-diene was obtained in 87% yield due to the protonolysis
of the corresponding vinyl zinc reagent (entries 1, 2 and 7).
Increasing the amount of Pd(PPh3)4 in the reaction (2-
10 mol%) led to an increased yield of the desired (1E,3E)-
1,4-dibutyl-3-phenylsulfonylhepta-1,3,6-triene (4a). So,
5 mol% of Pd(PPh3)4 was used to catalyse the Negishi
coupling reaction to avoid a large amount of catalyst loading.
A series of alkenyl halides were subjected to the above
optimal reaction conditions (Scheme 1). The results are
summarised in Table 2. From Table 2, we can see that the
Negishi coupling reactions of the intermediates 2 with a
variety of alkenyl iodides proceeded smoothly in the presence
of 5 mol% Pd(PPh3)4 at 25°C to afford the corresponding
WHWUDVXEVWLWXWHGꢀ ROH¿QVꢀ 4a–k in good yields after 12 h.
Although the reactivity of alkenyl bromides was slightly lower
than that of alkenyl iodides, the Negishi coupling reactions of
the intermediates 2 with a variety of alkenyl bromides could
also proceed smoothly in the presence of 5 mol% Pd(PPh3)4
at 40°&ꢀWRꢀDIIRUGꢀWKHꢀFRUUHVSRQGLQJꢀWHWUDVXEVWLWXWHGꢀROH¿QVꢀLQꢀ
good yields after 24 h (entries 12–14). The scope of both the
acetylenic sulfones 1 and the alkenyl halides 3 is broad
It is well documented that the Negishi coupling reaction of
vinyl zinc reagents with alkenyl halides, in the presence of a
SDOODGLXPꢀFDWDO\VWꢁꢀRFFXUVꢀZLWKꢀUHWHQWLRQꢀRIꢀFRQ¿JXUDWLRQꢆ22,23
The (1EꢇꢂFRQ¿JXUDWLRQꢀRIꢀFRPSRXQGVꢀ4 has been shown by
1
their +ꢀ 105ꢀ VSHFWUDꢁꢀ ZKLFKꢀ VKRZꢀ Dꢀ GRXEOHWꢀ DWꢀ įꢀ ꢀ ꢈꢆꢉꢈ±
6.95 ppm with a coupling constant of 15.6–16.4 Hz; this is
also evidence of the retention of the EꢂFRQ¿JXUDWLRQꢀRIꢀ WKHꢀ
starting alkenyl halides. In addition, the (3EꢇꢂFRQ¿JXUDWLRQꢀRIꢀ
compound 4iꢀZDVꢀFRQ¿UPHGꢀE\ꢀ12(6<ꢀH[SHULPHQWVꢆꢀ7KHUHꢀ
ZDVꢀ Dꢀ FRUUHODWLRQꢀ EHWZHHQꢀ WKHꢀ DURPDWLFꢀ SURWRQVꢀ ꢊįꢀ ꢀ ꢋꢆꢋꢌꢀ
SSPꢇꢀDQGꢀWKHꢀDOO\OLFꢀSURWRQVꢀꢊįꢀ ꢀꢍꢆꢅꢈꢀSSPꢇꢀRIꢀWKHꢀEXW\OꢀJURXSꢆꢀ
$ꢀFRUUHODWLRQꢀEHWZHHQꢀWKHꢀYLQ\OLFꢀSURWRQꢀꢊįꢀ ꢀꢅꢆꢃꢅꢀSSPꢇꢀDQGꢀ
WKHꢀDOO\OLFꢀSURWRQVꢀꢊįꢀ ꢀꢍꢆꢎꢋꢀSSPꢇꢀRIꢀWKHꢀDOO\OꢀJURXSꢀZDVꢀDOVRꢀ
observed. The NOE results indicate that 4i has the expected
1-Phenylsulfonyl-1-hexyne and (E)-1-iodo-1-hexene were
chosen to optimise the reaction conditions and the results are
shown in Table 1. Among the palladium catalysts examined,
Pd(PPh3)4 was the most effective (entries 4–6). Both Pd(OAc)2
* Correspondent. E-mail: caimzhong@163.com

430 JOURNAL OF CHEMICAL RESEARCH 2008
R
SO2Ar
ZnBr
ZnBr
THF
reflux
SO2Ar
+
R
1
2
X
R
SO2Ar
(3)
R1
H
R1
Pd(PPh3)4 (5 mol%), 25-40°C
H
4
Scheme 1
Table 2 Synthesis of tetrasubstituted olefins containing a 1,3,6-triene structural unit
Entry
R
Ar
R1
X
Product
Yieldb/%
1
2
n-C4H9
n-C4H9
n-C4H9
Ph
Ph
n-C4H9
Ph
CH3OCH2
n-C4H9
Ph
CH3OCH2
n-C4H9
Ph
CH3OCH2
Ph
CH3OCH2
n-C4H9
CH3OCH2
Ph
Ia
Ia
4a
4b
4c
4d
4e
4f
83
86
75
87
85
78
84
86
79
87
77
81
75
83
Ph
3
Ph
Ia
4
Ph
Ia
5
Ph
Ph
Ia
6
Ph
Ph
Ia
7
n-C4H9
n-C4H9
n-C4H9
Ph
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
Ph
Ia
4g
4h
4i
8
Ia
9
Ia
10
11
12
13
14
Ia
4j
Ph
Ia
4k
4a
4f
n-C4H9
Ph
Br[c]
Br[c]
Br[c]
Ph
4-CH3C6H4
n-C4H9
4h
aThe Negishi reaction was performed with 1.0 mmol of 2, 1.0 mmol of 3, and 0.05 mmol of Pd(PPh3)4 at 25ꢀ°C for 12 h.
bIsolated yield based on 1 used.
cThe Negishi reaction was performed with 1.0 mmol of 2, 1.0 mmol of 3, and 0.05 mmol of Pd(PPh3)4 at 40ꢀ°C for 24 h.
The organic layer was combined and dried over MgSO4. After
¿OWUDWLRQꢀDQGꢀUHPRYDOꢀRIꢀVROYHQWꢀXQGHUꢀUHGXFHGꢀSUHVVXUHꢁꢀWKHꢀUHVLGXHꢀ
ZDVꢀSXUL¿HGꢀE\ꢀFROXPQꢀFKURPDWRJUDSK\ꢀRQꢀVLOLFDꢀJHOꢀꢊHOXHQWꢀꢐꢀOLJKWꢀ
petroleum ether/EtOAc, 9:1).
(1E,3EꢇꢂFRQ¿JXUDWLRQꢀDQGꢀWKHꢀFURVVꢂFRXSOLQJꢀUHDFWLRQꢀRIꢀWKHꢀ
intermediates 2 with alkenyl halides occurs with retention
RIꢀFRQ¿JXUDWLRQꢀRIꢀERWKꢀWKHꢀVWDUWLQJꢀLQWHUPHGLDWHVꢀ2 and the
alkenyl halides 3.
,QꢀVXPPDU\ꢁꢀDQꢀHI¿FLHQWꢀDQGꢀVWHUHRVHOHFWLYHꢀRQHꢂSRWꢀV\QWKHWLFꢀ
PHWKRGꢀIRUꢀWHWUDVXEVWLWXWHGꢀROH¿QVꢀKDVꢀEHHQꢀGHYHORSHGꢀE\ꢀWKHꢀ
allylzincation of acetylenic sulfones, followed by the Negishi
coupling reaction with alkenyl halides in the presence of a
palladium catalyst. The present method has the advantages
of readily available starting materials, straightforward and
simple procedures, mild reaction conditions and good yields.
7KHVHꢀ WHWUDVXEVWLWXWHGꢀ ROH¿QVꢀ PD\ꢀ EHꢀ SRWHQWLDOꢀ PDWHULDOVꢀ
in the synthesis of natural products and in other synthetic
transformations.
(1E,3E)-1,4-Dibutyl-3-phenylsulfonylhepta-1,3,6-triene (4a): Oil.
,5ꢀꢊQHDWꢇꢁꢀȞꢀFP-1: 3079, 2957, 2925, 1637, 1605, 1446, 1148, 1089,
1
725, 689; H NMR (400 MHz, CDCl3ꢇꢐꢀįꢀꢋꢆꢉꢄ±ꢋꢆꢉꢃꢀꢊPꢁꢀꢍ+ꢇꢁꢀꢋꢆꢈꢅ±
7.46 (m, 3H), 5.85 (d, Jꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢋꢍ±ꢈꢆꢅꢃꢀꢊPꢁꢀꢃ+ꢇꢁꢀꢈꢆꢈꢅꢀꢊGWꢁꢀ
Jꢀ ꢀꢃꢅꢆꢌꢁꢀꢋꢆꢍꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢌꢅ±ꢑꢆꢎꢑꢀꢊPꢁꢀꢍ+ꢇꢁꢀꢍꢆꢎꢋꢀꢊGꢁꢀJꢀ ꢀꢅꢆꢑꢀ+]ꢁꢀꢍ+ꢇꢁꢀ
2.68 (t, Jꢀ ꢀꢋꢆꢍꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢌꢈ±ꢃꢆꢎꢎꢀꢊPꢁꢀꢍ+ꢇꢁꢀꢃꢆꢑꢋ±ꢃꢆꢃꢎꢀꢊPꢁꢀꢉ+ꢇꢁꢀꢌꢆꢎꢑ±
0.83 (m, 6H); 13C NMR (100 MHz, CDCl3ꢇꢐꢀįꢀꢃꢈꢄꢆꢍꢁꢀꢃꢑꢍꢆꢌꢁꢀꢃꢑꢌꢆꢉꢁꢀ
136.2, 134.4, 132.7, 128.7, 127.6, 122.3, 117.2, 39.8, 32.6, 31.8,
31.2, 30.9, 23.2, 22.2, 13.9, 13.8; MS (EI): m/z (%) 346 (M+, 5.7),
161 (24), 119 (33), 105 (58), 91 (100), 77 (83), 55 (51); Anal. Calcd.
for C21H30SO2: C, 72.79; H, 8.73. Found: C, 72.6; H, 8.6.
(1E,3E)-1-Phenyl-3-phenylsulfonyl-4-butylhepta-1,3,6-triene (4b):
2LOꢆꢀ ,5ꢀ ꢊQHDWꢇꢁꢀ Ȟꢀ FP-1: 3060, 2957, 2929, 1599, 1446, 1304, 1147,
1
1087, 726, 690; H NMR (400 MHz, CDCl3ꢇꢐꢀįꢀꢋꢆꢉꢈ±ꢋꢆꢉꢄꢀꢊPꢁꢀꢍ+ꢇꢁꢀ
Experimental
7.57–7.43 (m, 3H), 7.31–7.22 (m, 5H), 6.62 (d, Jꢀ ꢀꢃꢅꢆꢑꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢅꢆꢑꢎꢀ
(d, Jꢀ ꢀꢃꢅꢆꢑꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢋꢉ±ꢈꢆꢅꢋꢀꢊPꢁꢀꢃ+ꢇꢁꢀꢈꢆꢌꢎ±ꢑꢆꢎꢅꢀꢊPꢁꢀꢍ+ꢇꢁꢀꢄꢆꢌꢑꢀꢊGꢁꢀ
Jꢀ ꢀꢅꢆꢑꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢋꢄꢀꢊWꢁꢀJꢀ ꢀꢋꢆꢅꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢃꢆꢈꢍ±ꢃꢆꢄꢋꢀꢊPꢁꢀꢑ+ꢇꢁꢀꢌꢆꢎꢑꢀꢊWꢁꢀ
Jꢀ ꢀꢋꢆꢍꢀ+]ꢁꢀꢄ+ꢇꢒꢀ13C NMR (100 MHz, CDCl3ꢇꢐꢀįꢀꢃꢈꢑꢆꢄꢁꢀꢃꢑꢍꢆꢌꢁꢀꢃꢄꢋꢆꢅꢁꢀ
136.3, 134.3, 132.9, 132.2, 128.9, 128.7, 128.4, 127.6, 126.7, 121.4,
117.5, 40.0, 32.3, 31.2, 23.2, 13.9; MS (EI): m/z (%) 366 (M+, 6.5),
235 (34), 143 (42), 125 (52), 123 (64), 91 (57), 81 (86), 77 (100); Anal.
Calcd. for C23H26SO2: C, 75.37; H, 7.15. Found: C, 75.6; H, 7.2.
(1E,3E)-1-Methoxymethyl-3-phenylsulfonyl-4-butylhepta-1,3,6-
triene (4c): 2LOꢆꢀ ,5ꢀ ꢊQHDWꢇꢁꢀ Ȟꢀ FP-1: 3057, 2920, 2852, 1732, 1583,
THF was distilled from sodium immediately prior to use. IR spectra
ZHUHꢀ REWDLQHGꢀ ZLWKꢀ Dꢀ 3HUNLQꢂ(OPHUꢀ ꢅꢉꢄꢀ LQVWUXPHQWꢀ DVꢀ QHDWꢀ ¿OPVꢆꢀ
1H NMR spectra were recorded with a Bruker AC-400 (400 MHz)
spectrometer using CDCl3 as solvent. 13C NMR spectra were recorded
with a Bruker AC-400 (100 MHz) spectrometer using CDCl3 as
solvent. Mass spectra (EI) were determined with a Finnigan 8230
mass spectrometer. Microanalyses were measured with a Yanaco
MT-3 CHN microelemental analyser. Pd(PPh3)4 was prepared
according to a literature procedure.24 (For AA'XX' systems in
1H NMR, Jꢏꢀ ꢀJ23 + J25.)
1
1447, 1307, 1148, 1088, 725, 690; H NMR (400 MHz, CDCl3ꢇꢐꢀįꢀ
7.84–7.82 (m, 2H), 7.55–7.43 (m, 3H), 6.18 (d, Jꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀ
5.72–5.63 (m, 2H), 5.07–4.95 (m, 2H), 3.92 (d, Jꢀ ꢀꢈꢆꢅꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢄꢆꢍꢅꢀ
(s, 3H), 2.98 (d, Jꢀ ꢀꢅꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢅꢅꢀꢊWꢁꢀJꢀ ꢀꢋꢆꢍꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢃꢆꢑꢑ±ꢃꢆꢄꢍꢀ
(m, 4H), 0.93 (t, Jꢀ ꢀ ꢋꢆꢍꢀ +]ꢁꢀ ꢄ+ꢇꢒꢀ 13C NMR (100 MHz, CDCl3):
įꢀꢃꢈꢑꢆꢄꢁꢀꢃꢄꢈꢆꢅꢁꢀꢃꢄꢑꢆꢃꢁꢀꢃꢄꢍꢆꢎꢁꢀꢃꢍꢎꢆꢃꢁꢀꢃꢍꢉꢆꢎꢁꢀꢃꢍꢉꢆꢈꢁꢀꢃꢍꢋꢆꢑꢁꢀꢃꢍꢑꢆꢈꢁꢀꢃꢃꢋꢆꢈꢁꢀ
72.4, 58.1, 39.8, 32.1, 31.1, 23.2, 13.9; MS (EI): m/z (%) 334 (M+,
1.7), 277 (33), 161 (35), 117 (45), 105 (63), 91 (100), 77 (98); Anal.
Calcd. for C19H26SO3: C, 68.23; H, 7.84. Found: C, 68.5; H, 8.0.
(1E,3Z)-1-Butyl-3-phenylsulfonyl-4-phenyl-hepta-1,3,6-triene
(4d): 2LOꢆꢀ,5ꢀꢊQHDWꢇꢁꢀȞꢀFP-1: 3062, 2921, 2852, 1722, 1638, 1594, 1446,
1305, 1149, 1084, 754, 689; 1H NMR (400 MHz, CDCl3ꢇꢐꢀįꢀꢋꢆꢑꢎ±ꢋꢆꢑꢄꢀ
(m, 3H), 7.34–7.22 (m, 5H), 7.00–6.96 (m, 2H), 6.16 (d, Jꢀ ꢀꢃꢈꢆꢅꢀ+]ꢁꢀ
*HQHUDOꢀSURFHGXUHꢀIRUꢀWKHꢀV\QWKHVLVꢀRIꢀWHWUDVXEVWLWXWHGꢀROH¿QV 4a–k
$ꢀ 6FKOHQNꢀ ÀDVNꢀ ZLWKꢀ Dꢀ FRQGHQVHUꢀ ZDVꢀ FKDUJHGꢀ ZLWKꢀ GU\ꢀ 7+)ꢀ
(4.0 ml), activated zinc dust (92 mg, 1.4 mmol), and allyl bromide
(0.12 ml, 1.4 mmol) under an argon atmosphere. The mixture
was stirred at 0°C until the zinc dust disappeared (about 1.5 h).
Acetylenic sulfone (1.0 mmol) was added and the reaction mixture
ZDVꢀVWLUUHGꢀIRUꢀꢍ±ꢍꢆꢈꢀKꢀDWꢀUHÀX[ꢀWHPSHUDWXUHꢆꢀ7KHꢀUHDFWLRQꢀPL[WXUHꢀ
was then cooled to 25°C, and alkenyl iodide (1.0 mmol), Pd(PPh3)4
(58 mg, 5 mol%), and 4.0 ml of THF were added successively.
The mixture was stirred at 25°C for 12 h, quenched with a saturated
NH4Cl solution and extracted with diethyl ether (3 × 20 ml).

JOURNAL OF CHEMICAL RESEARCH 2008 431
1H), 5.91 (dt, Jꢀ ꢀꢃꢈꢆꢅꢁꢀꢋꢆꢍꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢅꢌ±ꢈꢆꢑꢎꢀꢊPꢁꢀꢃ+ꢇꢁꢀꢑꢆꢎꢎ±ꢑꢆꢉꢋꢀ
(m, 2H), 3.22 (d, Jꢀ ꢀ ꢅꢆꢑꢀ +]ꢁꢀ ꢍ+ꢇꢁꢀ ꢍꢆꢍꢍ±ꢍꢆꢃꢅꢀ ꢊPꢁꢀ ꢍ+ꢇꢁꢀ ꢃꢆꢑꢄ±ꢃꢆꢍꢃꢀ
(m, 4H), 0.92 (t, Jꢀ ꢀ ꢋꢆꢍꢀ +]ꢁꢀ ꢄ+ꢇꢒꢀ 13C NMR (100 MHz, CDCl3):
įꢀꢃꢈꢌꢆꢌꢁꢀꢃꢑꢃꢆꢎꢁꢀꢃꢑꢃꢆꢈꢁꢀꢃꢄꢎꢆꢈꢁꢀꢃꢄꢉꢆꢅꢁꢀꢃꢄꢄꢆꢑꢁꢀꢃꢄꢍꢆꢑꢁꢀꢃꢍꢉꢆꢄꢁꢀꢃꢍꢉꢆꢍꢁꢀꢃꢍꢋꢆꢎꢁꢀ
127.6, 121.6, 117.6, 43.5, 32.9, 31.0, 22.3, 13.9; MS (EI): m/z (%)
366 (M+, 6.8), 225 (61), 181 (55), 167 (84), 141 (80), 115 (67), 91
(100), 77 (54); Anal. Calcd. for C23H26SO2: C, 75.37; H, 7.15. Found:
C, 75.1; H, 7.05.
(1E,3Z)-1,4-Diphenyl-3-[(4-methylphenyl)sulfonyl] hepta-1,3,6-
triene (4j): 2LOꢆꢀ,5ꢀꢊQHDWꢇꢁꢀȞꢀFP-1: 3059, 2923, 1596, 1491, 1443, 1315,
1
1302, 1147, 1085, 813, 699; H NMR (400 MHz, CDCl3ꢇꢐꢀįꢀꢋꢆꢑꢉ±
7.21 (m, 12H), 7.04–7.01 (m, 2H), 6.94 (d, Jꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢅꢆꢉꢍꢀ
(d, Jꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢅꢄ±ꢈꢆꢈꢑꢀꢊPꢁꢀꢃ+ꢇꢁꢀꢈꢆꢌꢅ±ꢑꢆꢎꢍꢀꢊPꢁꢀꢍ+ꢇꢁꢀꢄꢆꢍꢎꢀꢊGꢁꢀ
Jꢀ ꢀꢅꢆꢉꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢄꢈꢀꢊVꢁꢀꢄ+ꢇꢒꢀ13C NMR (100 MHz, CDCl3ꢇꢐꢀįꢀꢃꢈꢌꢆꢋꢁꢀ
143.8, 139.8, 138.5, 136.2, 133.5, 132.3, 129.8, 128.8, 128.4, 128.2,
128.0, 127.9, 127.8, 127.7, 127.0, 120.7, 117.7, 43.9, 21.6; MS (EI):
m/z (%) 400 (M+, 22), 245 (91), 229 (55), 202 (93), 165 (55), 115
(47), 91 (100); Anal. Calcd. for C26H24SO2: C, 77.97; H, 6.04. Found:
C, 77.7; H, 5.8.
(1E,3Z)-1,4-Diphenyl-3-phenylsulfonylhepta-1,3,6-triene (4e): Oil.
,5ꢀꢊQHDWꢇꢁꢀȞꢀFP-1: 3059, 2922, 1594, 1490, 1447, 1305, 1148, 1084,
748, 689; 1H NMR (400 MHz, CDCl3ꢇꢐꢀįꢀꢋꢆꢈꢌ±ꢋꢆꢍꢍꢀꢊPꢁꢀꢃꢄ+ꢇꢁꢀꢋꢆꢌꢄ±
7.00 (m, 2H), 6.95 (d, Jꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢅꢆꢉꢄꢀꢊGꢁꢀJꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀ
(1E,3Z)-1-Methoxymethyl-3-[(4-methylphenyl)sulfonyl]-4-
phenylhepta-1,3,6-triene(4k):2LOꢆꢀ,5ꢀꢊQHDWꢇꢁꢀȞꢀFP-1:3079, 2923, 1728,
1637, 1596, 1443, 1318, 1150, 1086, 813, 700; 1H NMR (400 MHz,
CDCl3ꢇꢐꢀįꢀꢋꢆꢄꢄꢀꢊPꢁꢀJ*ꢀ ꢀꢉꢆꢑꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢋꢆꢍꢋ±ꢋꢆꢍꢍꢀꢊPꢁꢀꢄ+ꢇꢁꢀꢋꢆꢃꢌꢀꢊPꢁꢀ
J*ꢀ ꢀꢉꢆꢑꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢅꢆꢎꢉ±ꢅꢆꢎꢅꢀꢊPꢁꢀꢍ+ꢇꢁꢀꢅꢆꢑꢑꢀꢊGꢁꢀJꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢅꢆꢌꢄꢀ
(dt, Jꢀ ꢀꢃꢅꢆꢌꢁꢀꢈꢆꢅꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢅꢌ±ꢈꢆꢈꢌꢀꢊPꢁꢀꢃ+ꢇꢁꢀꢈꢆꢌꢃ±ꢑꢆꢉꢎꢀꢊPꢁꢀꢍ+ꢇꢁꢀ
4.07 (d, Jꢀ ꢀꢈꢆꢅꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢄꢆꢄꢉꢀꢊVꢁꢀꢄ+ꢇꢁꢀꢄꢆꢍꢍꢀꢊGꢁꢀJꢀ ꢀꢅꢆꢑꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢄꢋꢀ
(s, 3H); 13C NMR (100 MHz, CDCl3ꢇꢐꢀįꢀꢃꢈꢌꢆꢅꢁꢀꢃꢑꢄꢆꢑꢁꢀꢃꢄꢎꢆꢌꢁꢀꢃꢄꢉꢆꢈꢁꢀ
136.5, 133.2, 129.1, 128.2, 127.9, 127.7, 127.5, 123.7, 117.8, 72.4,
58.3, 43.5, 21.6; MS (EI): m/z (%) 368 (M+, 1.2), 181 (100), 165
(37), 115 (28), 91 (31); Anal. Calcd. for C22H24SO3: C, 71.71; H,
6.57. Found: C, 71.4; H, 6.35.
5.64–5.53 (m, 1H), 5.03–4.93 (m, 2H), 3.30 (d, Jꢀ ꢀꢅꢆꢉꢀ+]ꢁꢀꢍ+ꢇꢒꢀ13
C
NMR (100 MHz, CDCl3ꢇꢐꢀįꢀꢃꢈꢃꢆꢌꢁꢀꢃꢑꢃꢆꢈꢁꢀꢃꢄꢎꢆꢉꢁꢀꢃꢄꢉꢆꢅꢁꢀꢃꢄꢅꢆꢃꢁꢀꢃꢄꢄꢆꢈꢁꢀ
132.7, 132.2, 129.6, 128.8, 128.5, 128.3, 127.9, 127.7, 127.0, 120.6,
117.8, 43.9; MS (EI): m/z (%) 386 (M+, 17), 294 (100), 277 (63), 245
(74), 202 (58), 183 (78), 141 (74), 115 (57), 91 (53), 77 (50); Anal.
Calcd. for C25H22SO2: C, 77.69; H, 5.74. Found: C, 77.5; H, 5.5.
(1E,3Z)-1-Methoxymethyl-3-phenylsulfonyl-4-phenylhepta-
1,3,6-triene (4f): 2LOꢆꢀ ,5ꢀ ꢊQHDWꢇꢁꢀ Ȟꢀ FP-1: 3079, 2924, 2852, 1593,
1446, 1305, 1148, 1085, 753, 689; 1H NMR (400 MHz, CDCl3):
įꢀꢋꢆꢑꢋ±ꢋꢆꢑꢄꢀꢊPꢁꢀꢄ+ꢇꢁꢀꢋꢆꢄꢍ±ꢋꢆꢃꢎꢀꢊPꢁꢀꢈ+ꢇꢁꢀꢅꢆꢎꢋ±ꢅꢆꢎꢑꢀꢊPꢁꢀꢍ+ꢇꢁꢀꢅꢆꢑꢋꢀꢊGꢁꢀ
Jꢀ ꢀꢃꢅꢆꢌꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢅꢆꢌꢋꢀꢊGWꢁꢀJꢀ ꢀꢃꢅꢆꢌꢁꢀꢈꢆꢍꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢅꢃ±ꢈꢆꢈꢌꢀꢊPꢁꢀꢃ+ꢇꢁꢀ
5.01–4.90 (m, 2H), 4.07 (d, Jꢀ ꢀꢈꢆꢍꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢄꢆꢄꢉꢀꢊVꢁꢀꢄ+ꢇꢁꢀꢄꢆꢍꢄꢀꢊGꢁꢀ
Jꢀ ꢀꢅꢆꢑꢀ+]ꢁꢀꢍ+ꢇꢒꢀ13C NMR (100 MHz, CDCl3ꢇꢐꢀįꢀꢃꢈꢃꢆꢌꢁꢀꢃꢑꢃꢆꢑꢁꢀꢃꢄꢉꢆꢎꢁꢀ
138.3, 136.6, 133.1, 132.6, 128.4, 128.2, 127.7, 127.6, 123.5, 117.9,
72.4, 58.3, 43.5; MS (EI): m/z (%) 354 (M+, 1.5), 182 (53), 181
(100), 165 (92), 153 (53), 141 (47), 115 (61), 77 (42); Anal. Calcd.
for C21H22SO3: C, 71.16; H, 6.23. Found: C, 71.4; H, 6.4.
Project 20462002 was supported by the National Natural
Science Foundation of China.
Received 27 April 2008; accepted 23 June 2008
Paper 08/5242 doi: 10.3184/030823408X338729
Published online: 21 August 2008
(1E,3E)-1,4-Dibutyl-3-[(4-methylphenyl)sulfonyl]hepta-1,3,6-
triene (4g): 2LOꢆꢀ ,5ꢀ ꢊQHDWꢇꢁꢀ Ȟꢀ FP-1: 3061, 2957, 2927, 1719, 1637,
1598, 1457, 1301, 1147, 1090, 813; 1H NMR (400 MHz, CDCl3):
įꢀꢋꢆꢅꢎꢀꢊPꢁꢀJ*ꢀ ꢀꢉꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢋꢆꢍꢋꢀꢊPꢁꢀJ*ꢀ ꢀꢉꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢈꢆꢉꢅꢀꢊGꢁꢀ
Jꢀ ꢀꢃꢈꢆꢅꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢋꢃ±ꢈꢆꢅꢌꢀꢊPꢁꢀꢃ+ꢇꢁꢀꢈꢆꢈꢈꢀꢊGWꢁꢀJꢀ ꢀꢃꢈꢆꢅꢁꢀꢋꢆꢍꢀ+]ꢁꢀꢃ+ꢇꢁꢀ
5.05–4.94 (m, 2H), 2.96 (d, Jꢀ ꢀꢅꢆꢑꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢅꢋꢀꢊWꢁꢀJꢀ ꢀꢋꢆꢍꢀ+]ꢁꢀ
2H), 2.42 (s, 3H), 2.05-1.98 (m, 2H), 1.48–1.21 (m, 8H), 0.94–0.86
(m, 6H); 13C NMR (100 MHz, CDCl3ꢇꢐꢀįꢀꢃꢈꢍꢆꢅꢁꢀꢃꢑꢄꢆꢈꢁꢀꢃꢑꢌꢆꢅꢁꢀꢃꢄꢎꢆꢃꢁꢀ
136.5, 134.5, 129.3, 127.7, 122.4, 117.2, 39.8, 32.7, 31.8, 31.2, 30.9,
23.2, 22.2, 21.6, 13.9, 13.8; MS (EI): m/z (%) 360 (M+, 5.5), 205
(21), 161 (28), 119 (36), 105 (64), 91 (100), 79 (62), 55 (52); Anal.
Calcd. for C22H32SO2: C, 73.29; H, 8.95. Found: C, 73.5; H, 9.1.
(1E,3E)-1-Phenyl-3-[(4-methylphenyl)sulfonyl]-4-butylhepta-
1,3,6-triene (4h): 2LOꢆꢀ ,5ꢀ ꢊQHDWꢇꢁꢀ Ȟꢀ FP-1: 3059, 3026, 1636, 1597,
1448, 1315, 1146, 1088, 813, 749, 693; 1H NMR (400 MHz, CDCl3):
įꢀꢋꢆꢋꢍꢀꢊPꢁꢀJ*ꢀ ꢀꢉꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢋꢆꢈꢃ±ꢋꢆꢍꢈꢀꢊPꢁꢀꢋ+ꢇꢁꢀꢅꢆꢅꢄꢀꢊGꢁꢀJꢀ ꢀꢃꢅꢆꢑꢀ+]ꢁꢀ
1H), 6.50 (d, Jꢀ ꢀꢃꢅꢆꢑꢀ+]ꢁꢀꢃ+ꢇꢁꢀꢈꢆꢋꢑ±ꢈꢆꢅꢅꢀꢊPꢁꢀꢃ+ꢇꢁꢀꢈꢆꢌꢎ±ꢑꢆꢎꢈꢀꢊPꢁꢀ
2H), 3.03 (d, Jꢀ ꢀꢅꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢋꢍꢀꢊWꢁꢀJꢀ ꢀꢋꢆꢅꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢄꢎꢀꢊVꢁꢀꢄ+ꢇꢁꢀ
1.52–1.36 (m, 4H), 0.94 (t, Jꢀ ꢀꢋꢆꢍꢀ+]ꢁꢀꢄ+ꢇꢒꢀ13C NMR (100 MHz,
CDCl3ꢇꢐꢀ įꢀ ꢃꢈꢄꢆꢉꢁꢀ ꢃꢑꢄꢆꢋꢁꢀ ꢃꢄꢋꢆꢑꢁꢀ ꢃꢄꢅꢆꢅꢁꢀ ꢃꢄꢑꢆꢑꢁꢀ ꢃꢄꢍꢆꢄꢁꢀ ꢃꢄꢍꢆꢍꢁꢀ ꢃꢍꢎꢆꢈꢁꢀ
128.7, 128.3, 127.7, 126.7, 121.6, 117.4, 40.0, 32.3, 31.2, 23.2, 21.6,
14.0; MS (EI): m/z (%) 380 (M+, 14), 294 (51), 225 (43), 183 (41),
167 (45), 123 (48), 91 (100); Anal. Calcd. for C24H28SO2: C, 75.75;
H, 7.42. Found: C, 75.5; H, 7.5.
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(1E,3E)-1-Methoxymethyl-3-[(4-methylphenyl)sulfonyl]-4-
butylhepta-1,3,6-triene (4i): 2LOꢆꢀ,5ꢀꢊQHDWꢇꢁꢀȞꢀFP-1: 3056, 2922, 2856,
1730, 1589, 1446, 1308, 1146, 1089, 815; 1H NMR (400 MHz,
CDCl3ꢇꢐꢀįꢀꢋꢆꢋꢌꢀꢊPꢁꢀJ*ꢀ ꢀꢉꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢋꢆꢍꢉꢀꢊPꢁꢀJ*ꢀ ꢀꢉꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢅꢆꢃꢅꢀ
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(d, Jꢀ ꢀꢈꢆꢅꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢄꢆꢍꢋꢀꢊVꢁꢀꢄ+ꢇꢁꢀꢍꢆꢎꢋꢀꢊGꢁꢀJꢀ ꢀꢅꢆꢌꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢅꢈꢀꢊWꢁꢀ
Jꢀ ꢀꢋꢆꢍꢀ+]ꢁꢀꢍ+ꢇꢁꢀꢍꢆꢑꢍꢀꢊVꢁꢀꢄ+ꢇꢁꢀꢃꢆꢑꢑ±ꢃꢆꢄꢄꢀꢊPꢁꢀꢑ+ꢇꢁꢀꢌꢆꢎꢍꢀꢊWꢁꢀJꢀ ꢀꢋꢆꢍꢀ+]ꢁꢀ
3H); 13C NMR (100 MHz, CDCl3ꢇꢐꢀ įꢀ ꢃꢈꢄꢆꢋꢁꢀ ꢃꢑꢄꢆꢋꢁꢀ ꢃꢄꢎꢆꢍꢁꢀ ꢃꢄꢈꢆꢉꢁꢀ
135.5, 134.2, 129.4, 127.5, 124.6, 117.4, 72.4, 58.1, 39.7, 32.1, 31.1,
23.1, 21.6, 13.9; MS (EI): m/z (%) 348 (M+, 4.8), 161 (81), 139 (47),
131 (77), 105 (63), 91 (100); Anal. Calcd. for C20H28SO3: C, 68.93;
H, 8.10. Found: C, 68.6; H, 8.0.
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