C-C Bond Formation Using Organothio Groups
J . Org. Chem., Vol. 63, No. 17, 1998 5959
1.15-1.81 (m, 12 H), 3.44 (s, 3 H), 3.65 (m, 1 H), 4.55 (d, J )
11.4 Hz, 1 H), 4.69 (d, J ) 11.7 Hz, 1 H), 4.70 (d, J ) 3.9, 1
H), 7.26-7.48 (m, 10 H). 13C NMR (75 MHz, CDCl3): δ 13.99,
22.53, 25.41, 29.10, 29.45, 30.68, 31.71, 57.13, 72.70, 81.15,
95.81, 127.31, 127.65, 128.16, 128.36, 128.94, 129.03, 132.87,
135.53, 138.61. Anal. Calcd for C23H32O2S: C, 74.15; H, 8.66.
Found: C, 73.94, H; 8.82.
1-Meth oxy-1-p h en yl-3-bu ten e (8).20e 1H NMR (300 MHz,
CDCl3): δ 2.3-2.6 (m, 2 H), 3.22 (s, 3 H), 4.17 (t, 2 H), 2.26 (t,
J ) 6.0 Hz, 1 H), 5.0-5.15 (m, 2 H), 5.7-5.9 (m, 1 H), 7.1-7.6
(m, 5 H).
4-Met h oxy-5-(b en zyloxy)-1-d od ecen e (9). This com-
pound was isolated and characterized as a mixture of two
diastereomers (2:1); the ratio was determined by using 1H
NMR spectroscopy. 1H NMR (300 MHz, CDCl3): δ 0.88 (t, J
) 6.9 Hz, 3 H), 1.27 (br, 10 H), 1.4-1.5 (m, 2 H), 2.1-2.4 (m,
2 H), 3.1-3.2 (m, 1 H), 3.41 (s) and 3.42 (s) (total 3 H), 4.60
(m, 2 H), 5.0-5.1 (m, 2 H), 5.75-5.9 (m, 1 H), 7.1-7.6 (m, 5
H). 13C NMR (75 MHz, CDCl3): δ 14.03, 22.60, 25.71, 25.89,
29.20, 29.69, 29.86, 30.34, 31.79, 34.40, 34.74, 58.10, 58.44,
72.23, 72.74, 79.86, 82.25, 82.80, 116.72, 127.64, 127.80,
128.10, 128.41, 135.76, 139.05. MS (EI, m/e (%)): 304 (M+,
11), 219 (10), 197 (30), 154 (25). HRMS (EI). Calcd for
syn -1-Meth oxy-1-((4-m eth oxyp h en yl)th io)-2-(ben zylox-
y)n on a n e (4d ). 1H NMR (300 MHz, CDCl3): δ 0.88 (t, J )
6.0 Hz, 3 H), 1.24 (br, 9 H), 1.35-1.50 (m, 1 H), 1.58-1.70 (m,
1 H), 1.75-1.90 (m, 1 H), 3.4-3.5 (m, 1 H), 3.50 (s, 3 H), 3.81
(s, 3 H), 4.48 (d, J ) 11.1 Hz, 1 H), 4.53 (d, J ) 6.0 Hz, 1 H),
4.69 (d, J ) 11.1 Hz, 1 H), 6.84 (d, J ) 8.7 Hz, 2 H), 7.20-7.38
(m, 5 H), 7.44 (d, J ) 8.7 Hz, 2 H). 13C NMR (75 MHz,
CDCl3): δ 13.99, 22.54, 25.45, 29.13, 29.46, 31.34, 31.72, 55.25,
56.87, 73.54, 81.17, 95.55, 114.48, 124.49, 127.57, 128.15,
128.30, 135.94, 138.78, 159.69. Anal. Calcd for C24H34O3S:
C, 71.60; H, 8.51. Found: C, 71.34, H; 8.36.
C
20H32O2: 304.2402. Found: 304.2390.
4-Meth oxytetr a d eca n -2-on e (10). 1H NMR (300 MHz,
CDCl3): δ 0.88 (t, J ) 6.9 Hz, 3 H), 1.27 (br, 16 H), 1.4-1.5
(m, 2 H), 2.18 (s, 3 H), 2.2-2.3 (m, 1 H), 2.6-2.7 (m, 1 H),
3.32 (s, 3 H), 3.60-3.72 (m, 1 H). 13C NMR (75 MHz, CDCl3):
δ 13.99, 22.57, 24.97, 29.24, 29.49, 29.61, 31.01, 31.82, 33.73,
48.18, 56.85, 208.09. IR (neat): 1719 cm-1 (C)O). MS (EI,
m/e (%)): 242 (M+, 10), 227 (35), 210 (12), 185 (20). HRMS
(EI). Calcd for C15H30O2: 242.2245. Found: 242.2243.
1-Cya n o-1-m eth oxyu n d eca n e (11). 1H NMR (300 MHz,
CDCl3): δ 0.88 (t, J ) 6.9 Hz, 3H), 1.27 (br, 16 H), 1.4-1.5
(m, 2 H), 1.7-1.8 (m, 2 H), 3.48 (s, 3 H), 4.04 (t, J ) 6.6 Hz, 1
H). 13C NMR (75 MHz, CDCl3): δ 22.53, 24.55, 28.86, 29.16,
29.21, 29.33, 29.42, 31.76, 33.23, 57.83, 70.68, 118.23. Anal.
Calcd for C13H25NO: C, 73.88; H, 11.92; N, 6.63. Found: C,
74.15; H, 11.67; N, 6.62.
((4-Meth oxyp h en yl)th io)ben zyl Meth yl Eth er (6). To
a solution of 4-methoxybenzenethiol (1.23 mL, 10.0 mmol) and
triethylamine (1.60 mL, 11.5 mmol) in CCl4 (70 mL) was added
tributyltin chloride (2.70 mL, 10.0 mmol) at room temperature,
and the mixture was stirred at the same temperature over-
night. The removal of the solvent gave (4-methoxyphenylthio)-
tributylstannane (5.00 g), and this material was used for the
subsequent reaction without further purification.
To a solution of (4-methoxyphenylthio)tributylstannane (960
mg, 1.92 mmol) and benzaldehyde dimethyl acetal (0.30 mL,
2.0 mmol) in toluene/hexane (8/3, 11 mL) was added BF3‚OEt2
(0.25 mL, 2.0 mmol) at -78 °C. The mixture was stirred at
the same temperature for 8 h. Pyridine (0.5 mL) was added,
and the mixture was warmed to room temperature. A 2 N
aqueous NaOH solution (2.0 mL) was added, and the organic
materials were extracted with ether. The organic phase was
separated and washed with 1 N aqueous NaOH, water, and
brine and dried over Na2SO4. After removal of the solvent,
the residue was purified via flash chromatography (hexane/
EtOAc, 30/1) to obtain the title compound (347 mg, 67%).
TLC: Rf 0.45 (hexane/EtOAc, 10/1). 1H NMR (300 MHz,
CDCl3): δ 3.54 (s, 3 H), 3.77 (s, 3 H), 5.59 (s, 1 H), 6.81-6.90
(m, 2 H), 7.15-7.25 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ
55.17, 56.46, 91.57, 114.10, 122.71, 126.20, 127.72, 127.98,
136,73, 139.58, 159.97. Anal. Calcd for C15H16O2S: C, 69.20;
H, 6.19. Found: C, 69.08, H; 6.18.
1-Cya n o-1-((4-m eth oxyp h en yl)th io)u n d eca n e (12). 1H
NMR (300 MHz, CDCl3): δ 0.88 (t, J ) 7.2 Hz, 3 H), 1.26 (br,
16 H), 1.4-1.5 (m, 2 H), 1.7-1.8 (m, 2 H), 3.56 (t, J ) 7.5 Hz,
1 H), 3.83 (s, 3 H), 6.91 (d, J ) 6.6 Hz, 2 H), 7.56 (d, J ) 6.6
Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ 13.97, 22.54, 26.92,
28.68, 29.16, 29.34, 29.41, 31.77, 32.23, 37.79, 55.31, 114.99,
119.51, 120.97, 137.42, 161.21. Anal. Calcd for C19H29NOS:
C, 71.42; H, 9.15. Found: C, 71.35; H, 9.44.
1-Cyan o-1-m eth oxy-2-(ben zyloxy)n on an e (13). This com-
pound was characterized as a mixture of two diatereomers (1:
1
1), and the ratio was determined by using H NMR spectros-
copy. 1H NMR (300 MHz, CDCl3): δ 0.88 (t, J ) 0.88 Hz, 3
H), 1.50-1.80 (m, 12 H), 3.51 (s) and 3.52 (s) (total 3 H), 3.58-
3.70 (m, 1 H), 4.03 (d, J ) 5.4 Hz) and 4.11 (d, J ) 5.4 Hz)
(total 1 H), 4.607 (d, J ) 11.7 Hz) and 4.614 (d, J ) 11.4 Hz)
(total 1 H), 4.71 (d, J ) 11.7 Hz) and 4.79 (d, J ) 11.4 Hz)
(total 1 H), 7.22-7.42 (m, 5 H). 13C NMR (75 MHz, CDCl3):
δ 13.95, 22.50, 24.81, 25.12, 29.01, 29.30, 30.73, 31.09, 31.65,
58.46, 58.54, 73.51, 73.86, 74.31, 78.41, 78.49, 116.76, 117.05,
127.98, 128.03, 128.07, 128.18, 128.50, 128.53, 137.83. Anal.
Calcd for C18H27NO2: C, 74.70; H, 9.40; N, 4.84. Found: C,
74.42; H, 9.48, N, 4.55.
Electr ooxidative In ter m olecu lar Car bon -Car bon Bon d
F or m a tion . Gen er a l P r oced u r e. To an undivided cell
equipped with a carbon rod electrode (i.d. ) 4 mm), a platinum
plate cathode (2 × 3 cm), and a magnetic stirring bar was
placed dried molecular sieves 4 Å (ca. 160 mg). The supporting
electrolyte (0.20 mmol), the substrate (0.50 mmol), the nu-
cleophile (1.0-2.5 mmol), and dichloromethane (1.0 mL) were
added. A constant current (10 mA) was passed under an
atmosphere of nitrogen. After most of the substrate was
consumed (determined by TLC), the current was turned off,
and the reaction mixture was transferred to a flask. After
removal of the solvent, the crude materials were passed
through a short (5 cm) column of silica gel (ether elution) to
remove the supporting electrolyte. The crude product thus
obtained was purified with flash chromatography. Sometimes
the sulfur containing byproducts contaminated the desired
product. In such a case, the crude product was treated with
a small amount of m-chloroperoxybenzoic acid at 0 °C for ca.
5 min to oxidize the sulfur-containing byproducts. The
oxidized sulfur-containing byproducts were easily separable
by flash chromatography.
4-((Meth ylth io)m eth oxy)-1-u n d ecen e (14). To a solution
of allylmagnesium bromide in THF (0.77 M, 60.0 mL, 46.2
mmol) was added dropwise to a solution of octanal (6.0 mL,
38.4 mmol) in THF (10 mL) at 0 °C. The mixture was refluxed
for 0.5 h and cooled to room temperature. Saturated aqueous
NH4Cl (9.6 mL) was added, and solid materials were removed
by filtration. The solvent was evaporated and the residue was
purified by distillation (71-74 °C, 1.2 mmHg) to obtain
1-undecen-4-ol6a (4.98 g, 76%). TLC: Rf 0.25 (hexane/EtOAc,-
10/1). GC: Rt 2.43 min (OV-1 25 m, capillary 100-150 °C, 10
°C/min). 1H NMR (300 MHz, CDCl3): δ 0.88 (t, J ) 6.3 Hz, 3
H), 1.28 (br s, 11 H), 1.4-1.5 (m, 2 H), 2.05-2.10 (m, 1 H),
2.20-2.38 (m, 1 H), 3.64 (br, 1 H), 5.11-5.17 (m, 2 H), 5.76-
5.95 (m, 1 H). 13C NMR (75 MHz, CDCl3): δ 13.95, 22.53,
23.23, 29.15, 30.00, 31.71, 39.08, 43.60, 73.45, 118.61, 133.92.
To a suspension of silver nitrate (930 mg, 5.5 mmol) and
triethylamine (0.83 mL, 6.0 mmol) in benzene (25 mL) was
added a solution of 1-undecen-4-ol (884 mg, 5.0 mmol) and
chloromethyl methyl sulfide (0.50 mL, 6.0 mmol) in benzene
(2.5 mL). The mixture was heated at 60 °C for 17 h. The
reaction mixture was filtered, and the filtrate was washed with
4-Meth oxy-1-tetr a d ecen e (7). GLC: Rt 9.65 min (OV-1
o
25 m, 100-250 °C, 10 C/min). 1H NMR (300 MHz, CDCl3): δ
0.88 (t, J ) 6.9 Hz, 3 H), 1.27 (br, 16 H), 1.4-1.5 (m, 2 H),
2.26 (t, J ) 6.0 Hz, 2 H), 3.34 (s, 3 H), 5.0-5.15 (m, 2 H), 5.7-
5.9 (m, 1 H). 13C NMR (75 MHz, CDCl3): δ 13.98, 22.57, 25.17,
29.24, 29.53, 29.69, 31.82, 33.29, 37.69, 56.47, 80.54, 116.76,
135.15. Anal. Calcd for C15H30O: C, 79.58; H, 13.36. Found:
C, 79.68, H; 13.65.