Notes
J . Org. Chem., Vol. 63, No. 23, 1998 8607
Ta ble 1. [2+2+2] Cocycliza tion of Dia lk yn e a n d Alk yn e
J ) 6.9, 2.0 Hz, 2 H), 2.37 (s, 3 H), 1.80 (tt, J ) 6.9, 6.9 Hz, 2
H), 1.35 (s, 9 H); EI-MS m/z (%); 451 (M+, 0.2), 350 (0.7), 155
(16.7), 115 (15.7), 91 (51.9), 57 (78.1), 41 (100.0); EI-HRMS calcd
for C26H29O4NS 451.1819, found 451.1807.
N-(8-P h en yl-2,7-octa d iyn yl)-p-tolu en esu lfon a m id e: To a
solution of N-tert-butoxycarbonyl-N-(8-phenyl-2,7-octadiynyl)-p-
toluenesulfonamide (1.63 g, 3.62 mmol) in CH2Cl2 (9 mL), was
added trifluoroacetic acid (TFA) (1.4 mL, 18.4 mmol) at 0 °C.
After 4 h, the reaction was quenched by the addition of aq.
NaHCO3. The water layer was extracted with AcOEt. The
organic extracts were washed with brine, dried over Na2SO4,
concentrated, and chromatographed (hexane:AcOEt ) 9:2) to
give N-(8-phenyl-2,7-octadiynyl)-p-toluenesulfonamide (1.14 g,
90%): IR (KBr) 3050, 2224, 1596, 1492, 1344, 1154, 758, 690
cm-1; 1H NMR (270 MHz, CDCl3, TMS) δ 7.77 (d, J ) 8.6 Hz, 2
H), 7.40-7.36 (m, 2 H), 7.33-7.26 (m, 5 H), 4.55 (t, J ) 5.9 Hz,
1 H), 3.82 (dt, J ) 5.9, 2.0 Hz, 2 H), 2.41 (s, 3 H), 2.36 (t, J ) 6.9
Hz, 2 H), 2.16 (tt, J ) 6.9, 2.0 Hz, 2 H), 1.60 (tt, J ) 6.9, 6.9 Hz,
2 H); EI-MS m/z (%); 351 (M+, 2.4), 350 (8.3), 196 (65.2), 115
(38.7), 91 (100.0); EI-HRMS calcd for C21H21O2NS 351.1294,
found 351.1279.
N-2-Bu t yn yl-N-(8-p h en yl-2,7-oct a d iyn yl)-p -t olu en esu l-
fon a m id e (5) (n ) 1): To a solution of p-toluenesulfonamide
(1.06 g, 3.03 mmol) in DMF (7 mL), was added NaH (60%
dispersion, 138 mg, 3.64 mmol) at 0 °C. After 40 min at room
temprature, a solution of 1-methansulfoxy-2-butyne (586 mg,
3.84 mmol) in DMF (13 mL) was added. The reaction mixture
was stirred for 1.5 h and quenched by the addition of aq. NH4Cl
at 0 °C. The water layer was extracted with ether. The
combined ether extracts were washed with brine, dried over Na2-
SO4, concentrated, and chromatographed (hexane:AcOEt ) 50:
1-20:1) to give 5 (n ) 1) (1.03 g, 84%). 5 (n ) 1): IR (neat)
2228, 1598, 1490, 1350, 1164, 758, 658 cm-1; 1H NMR (270 MHz,
CDCl3, TMS) δ 7.74-7.70 (m, 2 H), 7.40-7.36 (m, 2 H), 7.30-
7.26 (m, 5 H), 4.13 (t, J ) 2.0 Hz, 2 H), 4.08 (q, J ) 2.3 Hz, 2 H),
2.40 (s, 3 H), 2.39 (t, J ) 6.9 Hz, 2 H), 2.20 (tt, J ) 6.9, 2.0 Hz,
2 H), 1.67 (t, J ) 2.3 Hz, 3 H), 1.63 (tt, J ) 6.9, 6.9 Hz, 2 H);
EI-MS m/z (%); 403 (M+, 1.3), 248 (38.9), 221 (11.1), 167 (12.7),
155 (13.3), 129 (10.5), 115 (37.7), 91 (100.0), 77 (18.8); EI-HRMS
calcd for C25H25O2NS 403.1608, found 403.1616.
Mo(CO)6
mol %
run
R
R'
eq.
3 (%)
4 (%)
1
2
3
4
5
6
7
Et
Et
Et
Et
Et
Ph
Ph
Et
Et
Et
Et
Et
Ph
Me
2
5
8
15
15
15
15
35
35
35
35
20
35
35
3a
3a
3a
3a
3a
3b
3c
10
25
34
44
43
43
49a
8
6
3
5
7
5
3
a
The reaction time was 100 min.
Ta ble 2. In tr a m olecu la r [2+2+2] Cocycliza tion
N-2-Butynyl-N-(9-phenyl-2,8-nonadiynyl)-p-toluenesulfona-
mide (5) (n ) 2) was prepared as discribed for 5 (n ) 2). 5 (n )
run
n
time (h)
6 (%)
2): IR (neat) 2232, 1598, 1490, 1350, 1162, 756, 658 cm-1 1H
;
1
2
1
2
2.0
2.5
44
37
NMR (270 MHz, CDCl3, TMS) δ 7.71 (d, J ) 8.6 Hz, 2 H), 7.41-
7.37 (m, 2 H), 7.29-7.26 (m, 5 H), 4.12 (t, J ) 2.0 Hz, 2 H), 4.07
(q, J ) 2.6 Hz, 2 H), 2.41 (s, 3 H), 2.38 (t, J ) 6.6 Hz, 2 H), 2.08
(tt, J ) 6.6, 2.0 Hz, 2 H), 1.65 (t, J ) 2.6 Hz, 3 H), 1.60-1.53
(m, 4 H); EI-MS m/z (%); 417 (M+, 1.3), 155 (14.3), 129 (10.7),
115 (41.4), 91 (100.0), 89 (10.2), 77 (16.3); EI-HRMS calcd for
C26H27O2NS 417.1764, found 417.1763.
dispersion, 1.58 g, 37.8 mmol) at 0 °C. After 25 min at room
temperature, a solution of 1-methansulfoxy-2-butyne (5.79 g,
39.1 mmol) in DMF (70 mL) was added. The reaction mixture
was stirred for 1 h and quenched by the addition of aq. NH4Cl.
The water layer was extracted with ether. The combined ether
extracts were washed with brine, dried over Na2SO4, concen-
trated, and chromatographed (hexane:AcOEt ) 4:1) to give 1
(4.17 g, 85%). 1: IR (KBr) 1346, 1332, 1162, 660 cm-1; 1H NMR
(270 MHz, CDCl3, TMS) δ 7.73-7.70 (m, 2 H), 7.30-7.27 (m, 2
H), 4.08 (q, J ) 2.3 Hz, 4 H), 2.42 (s, 3 H), 1.65 (t, J ) 2.3 Hz,
6H); 13C NMR (270 MHz, CDCl3) d 143.4 (C), 135.5 (C), 129.1
(CH), 127.9 (CH), 81.5 (C), 71.5 (C), 36.6 (CH2), 21.4 (CH3), 3.3
(CH3); EI-MS m/z (%); 275(M+, 1.5), 260 (35.3), 155 (24.6), 139
(16.7), 120 (87.2), 91 (100.0); EI-HRMS calcd for C15H17O2NS
275.0981, found 275.0973.
Gen er a l P r oced u r e (Ta ble 1, r u n 4). To a mixture of 1
(275 mg, 1 mmol), Mo(CO)6 (92.7 mg, 35 mmol, 35 mol %), and
p-chlorophenol (129 mg, 1 mmol) in degassed toluene (10 mL)
was added 3-hexyne (1.7 mL, 15 mmol). The whole reaction
mixture was refluxed for 210 min. After addition of ether, the
organic layer was washed with 10% NaOH and brine, dried over
Na2SO4, concentrated, and chromatographed (hexane:AcOEt )
30:1-15:1) to give 5,6-diethyl-4,7-dimethyl-2-p-toluenesulfonyl-
isoindoline (3a ) (158.4 mg, 44% yield) and 3(E),4(E)-diethylidene-
1-p-toluenesulfonylpyrrolidine (4) (14.5 mg, 5% yield). 3a : mp
175.5-176.5 °C (2-propanol). IR (Nujol) 2360, 2344, 1458, 1344,
P r ep a r a tion of N-2-Bu tyn yl-N-(8-p h en yl-2,7-octa d iyn yl)-
p -t olu en esu lfon a m id e (5) (n ) 1) a n d N-2-Bu t yn yl-N-(9-
p h en yl-2,8-n on a d iyn yl)-p-tolu en esu lfon a m id e (5) (n ) 2).
N-ter t-Bu toxyca r bon yl-N-(8-p h en yl-2,7-octa d iyn yl)-p-tolu -
en esu lfon a m id e: To a solution of N-tert-butoxycarbonyl-N-p-
toluenesulfonamide (1.06 g, 3.89 mmol), PPh3(1.02 g, 3.9 mmol),
and 8-pheny-2,7-octadiyn-1-ol (762 mg, 3.85 mmol) in tetrahy-
drofuran (THF) (9 mL) was added DEAD (0.71 mL, 3.91 mmol)
at 0 °C. After 2 h, the reaction was quenched by the addition of
aq. NH4Cl. The water layer was extracted with AcOEt. The
organic extracts were washed with brine, dried over Na2SO4,
concentrated, and chromatographed (hexane:AcOEt ) 6:1) to
give N-tert-butoxycarbonyl-N-(8-phenyl-2,7-octadiynyl)-p-tolu-
enesulfonamide (1.69 g, 97%): IR (neat) 2228, 1732, 1598, 1490,
1160 cm-1 1H NMR (270 MHz, CDCl3, TMS) δ 7.78 (d, J ) 7.9
.
Hz, 2 H), 7.30 (d, J ) 7.9 Hz, 2 H), 4.57 (s, 4 H), 2.62 (q, J ) 7.3
Hz, 4 H), 2.40 (s, 3 H), 2.12 (s, 6 H), 1.08 (t, J ) 7.3 Hz, 6 H).
13C NMR (400 MHZ, CDCl3) d 143.4 (C), 140.0 (C), 133.8 (C),
132.8 (C), 129.7 (CH), 127.8 (C), 127.5 (CH), 54.1 (CH2), 22.1
(CH2), 21.4 (CH3), 15.5 (CH3), 14.6 (CH3). EI-MS m/z (%); 357
(M+, 9.6), 342 (2.5), 202 (51.8), 201 (100.0), 186 (36.1), 172 (17.8),
158 (8.1), 91 (26.7). EI-HRMS calcd for C21H27O2NS 357.1764,
found 357.1785. Anal. Calcd for C21H27O2NS: C, 70.55; H, 7.61;
N, 3.92; S, 8.97. Found: C, 70.38; H, 7.56; N, 3.89; S, 9.01. 4:
mp 120-121 °C (hexane-benzene). IR (Nujol) 2360, 2342, 1670,
1456, 1340, 1164, 1098, 820 cm-1 1H NMR (270 MHz, CDCl3,
.
TMS) d 7.74 (d, J ) 8.3 Hz, 2 H), 7.33 (d, J ) 8.3 Hz, 2 H), 5.73
(q, J ) 6.6 Hz, 2 H), 3.94 (s, 4 H), 2.43 (s, 3 H), 1.63 (d, J ) 6.6
Hz, 6 H). 13C NMR (400 MHZ, CDCl3) d 143.6 (C), 134.4 (C),
133.1 (C), 129.7 (CH), 127.8 (CH), 114.0 (CH), 51.0 (CH2), 21.5
1362, 1154, 758, 674 cm-1; H NMR (270 MHz, CDCl3, TMS) δ
7.93 (d, J ) 8.2 Hz, 2 H), 7.40-7.37 (m, 2 H), 7.31-7.26 (m, 5
H), 4.62 (t, J ) 2.0 Hz, 2 H), 2.50 (t, J ) 6.9 Hz, 2 H), 2.40 (tt,
1