Ni-Catalyzed Electrochemical Couplings
J . Org. Chem., Vol. 65, No. 15, 2000 4583
thesis was run at constant current density (0.3 Adm-2). The
reaction was monitored by GC and stopped after alkenyl halide
was consumed (ca. 4.5 h). A charge of 2 F mole-1 was used in
most reactions described in this paper. The mixture was then
hydrolyzed with hydrochloric acid (1 N) and diluted with
diethyl ether. The aqueous layer was extracted with diethyl
ether, the combined organic layers were washed with water
and saturated NaCl solution, dried over MgSO4 and the solvent
was evaporated. The oil thus obtained was purified by column
chromatography to give desired compounds.40
126.4 (1C, sp2), 127.8 (1C, sp2), 128.3 (2C, sp2), 128.9 (2C,
sp2),129.1 (1C, sp2), 138.4 (1C, sp2), 151.4 (1C, sp2), 153.2 (1C,
sp2), 173.8 (1C, CO2); MS 326 (M base), 295 (M - OMe), 267
(M - CO2Me), 235 (M - 91).
Meth yl 2-(1-cyclopen ten yl)pr opan oate: 1H NMR (CDCl3,
200 MHz) δ 1.29 (3H, d J ) 7.0 Hz), 1.87 (2H, quint J ) 7.2
Hz), 2.30 (4H, m), 3.27 (1H, q J ) 7.0 Hz), 3.67 (3H, s), 5.51
(1H, m); 13C NMR (CDCl3, 50.3 MHz) 15.6 (1C, CH3), 23 (1C,
CH2), 32 (1C, CH2), 33 (1C, CH2), 41.2 (1C, CH), 51.3 (1C, CH3),
125.7 (1C, sp2), 142.3 (1C, sp2), 174.5 (1C, CO2); MS 154 (M),
95 (M - CO2Me base).
(E)-4-Meth yl 4-h exen -2-on e:50 1H NMR (CDCl3, 200 MHz)
δ 1.62 (3H, s), 1.64 (3H, d J ) 5.4 Hz), 2.13 (3H, s), 3.06 (2H,
s), 5.36 (1H, q J ) 5.4 Hz); 13C NMR (CDCl3, 50.3 MHz) 13.3
(1C, CH3), 15.6 (1C, CH3), 28.6 (1C, CH3), 54.4 (1C, CH2), 123.6
(1C, sp2), 129.3 (1C, sp2), 208 (1C, CO); MS 112 (M), 97 (M -
15 base), 69 (M - 43).
(E)-2-Meth yl-3-n on en oic a cid , m eth yl ester : 1H NMR
(CDCl3, 200 MHz) δ 0.88 (3H, t J ) 6.8 Hz), 1.22 (3H, d J )
7.0 Hz), 1.30-1.40 (6H, m), 2.0 (2H, td J ) 6.8 Hz J ) 6.5
Hz), 3.1 (1H, dq J ) 8.5 Hz J ) 7.0 Hz), 3.66 (3H, s), 5.41-
5.54 (2H, m); 13C NMR (CDCl3, 50.3 MHz) 13.4 (1C), 16.9 (1C),
21.9 (1C), 28.4 (1C), 31 (1C), 31.9 (1C), 42.3 (1C), 51.1 (1C),
128.4 (1C, sp2), 131.7 (1C, sp2), 174.9 (1C, CO2); MS 185 (M
base), 153, 88; IR 3060, 1750, 980 cm-1. Anal. Calcd for
Ch a r a cter iza tion of th e P r od u cts. (1E,3E)-1,4-Dip h en -
ylbu ta -1,3-d ien e. Characterization was done unequivocally
by comparison with the commercial sample.
(1Z,3Z)-1,4-Dip h en ylbu ta -1,3-d ien e. Identification and
characterization were achieved from a pure fraction of column
chromatography on silica gel: 1H NMR (CDCl3, 200 MHz) δ
7.44 (m, 10H), 6.75 (m, 4H); 13C NMR (CDCl3, 50.321 MHz) δ
126.8, 127.9, 128.6, 129.4, 132.3, 137.5; MS 206 (base), 129,
91, 77.
(6E,8E)-Tetr a d eca -6,8-d ien e: 1H NMR (CDCl3, 200 MHz)
δ 5.83-5.94 (m, 2H), 5.36-5.53 (m, 2H), 1.96 (q, J ) 7.0 Hz,
4H), 1.21-1.37 (m, 12H), 0.80 (t, J ) 6.5 Hz, 6H); 13C NMR
(50.321 MHz, CDCl3) δ 13.8, 22.3, 28.9, 31.2, 32.7, 130.2 (lit.48
130.3), 132.0 (lit.48 132.6); MS 194, 67 (base); IR 3020, 1470,
990, 970 cm-1
.
(6Z,8Z)-Tetr a d eca -6,8-d ien e:49 1H NMR (CDCl3, 200 MHz)
δ 6.18 (m, 2H), 5.35 (m, 2H), 1.91-2.13 (m, 4H), 1.19-1.39
(m, 12H), 0.80 (t, J ) 6.5 Hz, 6H); 13C NMR (50.321 MHz,
CDCl3) δ 13.8, 22.4, 27.3, 29.3, 31.4, 123.5, 131.7; MS 194, 67
(base).
C
11H20O2: C, 71.7; H, 10.94. Found: C, 71.84; H, 10.89.
(Z)-2-Meth yl-3-n on en oic a cid m eth yl ester : 1H NMR
(CDCl3, 200 MHz) δ 0.88 (3H, t J ) 6.8 Hz), 1.21 (3H, d J )
7.0 Hz), 1.30-1.40 (6H, m), 2.08 (2H, td J ) 6.9 Hz J ) 6.7
Hz), 3.43 (1H, dq J ) 8.5 Hz J ) 7.0 Hz), 3.65 (3H, s), 5.32-
5.44 (2H, m); 13C NMR (CDCl3, 50.3 MHz) 13.4 (1C), 17.5 (1C),
22.0 (1C), 26.7 (1C), 28.7 (1C), 31.0 (1C), 37.5 (1C), 51.0 (1C),
128.2 (1C, sp2), 131.3 (1C, sp2), 174.7 (1C, CO2); MS 185 (M
(6Z,8E)-Tetr a d eca -6,8-d ien e. Assigment was determi-
nated from a mixture of (E,E), (Z,Z), (E,Z) stereoisomers and
compared to literature data:48 13C NMR (50.321 MHz, CDCl3)
δ 125.5, 128.5, 129.8, 134.3 (lit.48 δ: 126.0, 129.0, 130.8, 134.8);
MS, 194, 67 (base).
base), 153, 110; IR 3040, 1750, 730 cm-1
.
(Z)-3-Meth yl-5-p h en yl-4-p en ten e-2-on e: 1H NMR (CDCl3,
200 MHz) δ 1.23 (3H, d J ) 6.85 Hz), 2.09 (3H, s), 3.72 (1H,
dq J ) 10.5 Hz J ) 6.85 Hz), 5.59 (1H, dd J ) 11.5 Hz J )
10.5 Hz), 6.6 (1H, d J ) 11.5 Hz), 7.21-7.39 (5H, m); 13C NMR
(CDCl3, 50.3 MHz) 17 (1C, CH3), 28 (1C, CH3), 46.6 (1C, CH),
127.2 (1C, sp2), 128.4 (4C, sp2), 131.1 (1C, sp2), 131.2 (1C, sp2),
136.7 (1C, sp2), 209.5 (1C, CO); MS 174 (M), 131 (M - 43 base),
116; IR 3030, 1740, 1610, 700 cm-1. Anal. Calcd for C12H14O:
C, 82.72; H, 8.09. Found: C, 82.74; H, 7.88.
The following compounds were identified by comparison of
their physical and spectral data with those given in the cited
references: (E)-3-butenoic acid, 4-phenyl methyl ester;51a (Z)-
3-butenoic acid, 4-phenyl methyl ester;51b (E)-3-butenoic acid,
2-methyl 4-phenyl methyl ester;26 (Z)-3-butenoic acid, 2-methyl
4-phenyl methyl ester;52 (E)-4-pentene-2-one, 3-methyl-5-phen-
yl;53 (E)-4-pentene-2-one, 5-phenyl;28 (Z)-4-pentene-2-one, 5-phen-
yl;28 (E)-3-butene nitrile, 2-methyl-4-phenyl;54 (E)-4-hexen-2-
one;55 (Z)-4-hexen-2-one;55 (Z)-4-methyl 4-hexen-2-one;56 (E)-
3-penten-1-one, 3-methyl-1-phenyl;57 (Z)-3-penten-1-one, 3-meth-
yl-1-phenyl;57 (E)-3-(2-phenylethenyl)thiophene;33c (Z)-3-(2-phenyl-
ethenyl)thiophene;58 (E)-2-(2-phenylethenyl)thiophene;59 (Z)-
2-(2-phenylethenyl)thiophene;60 (E)-3-(2-phenylethenyl)pyri-
dine;61 (Z)-3-(2-phenylethenyl)pyridine;33a (E)-2-(2-phenylethen-
yl)pyridine;62 (Z)-2-(2-phenylethenyl)pyridine.62
(Z)-2-Meth yl-4-p h en yl-3-bu ten en itr ile: 1H NMR (CDCl3,
200 MHz) δ 1.37 (3H, d J ) 6.9 Hz), 3.7 (1H, dq J ) 9.9 Hz J
) 6.9 Hz), 5.56 (1H, dd J ) 11 Hz J ) 9.9 Hz), 6.63 (1H, d J
) 11 Hz), 7.20-7.40 (5H, m); 13C NMR (CDCl3, 50.3 MHz) 19.2
(1C, CH3), 24.2 (1C, CH), 121.4 (1C), 126.8 (1C), 127.8 (1C),
128.4 (2C, sp2), 128.6 (2C, sp2), 132.7 (1C), 135.4 (1C); MS 157
(M base), 131 (M - CN), 114; IR 3015, 2245, 1610, 700 cm-1
.
Anal. Calcd for C11H11N: C, 84.04; H, 7.05; N, 8.91. Found:
C, 83.80; H, 7.02; N, 8.73.
(Z)-4-(2,5-Dim eth oxyp h en yl)-2-m eth yl-3-bu ten oic a cid ,
1
m eth yl ester : H NMR (CDCl3, 200 MHz) δ 1.27 (3H, d J )
J O000182F
6.8 Hz), 3.3 (1H, m), 3.67 (3H, s), 3.71 (3H, s), 3.74 (3H, s),
5.71 (1H, dd J ) 11.4 Hz J ) 10.3 Hz), 6.6 (1H, d J ) 11.4
Hz), 6.76-7.13 (3H, m); 13C NMR (CDCl3, 50.3 MHz) 18.0 (1C,
CH3), 38.9 (1C, CH), 51.5 (1C, CH3), 55.2 (1C, CH3), 55.6 (1C,
CH3), 111.2 (1C, sp2), 113.1 (1C, sp2), 115.4 (1C, sp2), 125.86
(1C, sp2), 125.93 (1C, sp2), 130.6 (1C, sp2), 151.1 (1C, sp2), 152.9
(1C, sp2), 174.9 (1C, CO2); MS 250 (M base), 191 (M - CO2-
Me).
(50) The Z and E assignments were confirmed by NOE effect.
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(Z)-4-(2,5-Dim eth oxyp h en yl)-2-ben zyl-3-bu ten oic a cid ,
1
m eth yl ester : H NMR (CDCl3, 200 MHz): δ 2.87 (1H, dd J
) 13.7 Hz J ) 7.0 Hz), 3.09 (1H, dd J ) 13.7 Hz J ) 7.8 Hz),
3.63 (3H, s), 3.70 (3H, s), 3.74 (3H, s), 3.75-3.89 (1H, m), 5.75
(1H, dd J ) 11.4 Hz J ) 10.4 Hz), 6.62 (1H, d J ) 11.4 Hz),
6.69-7.25 (8H, m); 13C NMR (CDCl3, 50.3 MHz) 39.1 (1C, CH),
46.8 (1C, CH2), 51.7 (1C, CH3), 55.5 (1C, CH3), 55.9 (1C, CH3),
111.7 (1C, sp2), 113.6 (1C, sp2), 115.4 (1C, sp2), 126.1 (1C, sp2),
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