Notes
J . Org. Chem., Vol. 66, No. 4, 2001 1507
dried over anhydrous Na2SO4. The solvent was removed under
reduced pressure to afford arylindanes 6a -6g or 7 or cyclopen-
tene carbothioate 8a , 11a , or 15a , which was purified by column
chromatography on silica gel using hexanes-ethyl acetate (97:
3) as eluent to obtain analytically pure product.
3H), 2.04 (ddt, J ) 18.1, 8.6, 3.0 Hz, 1H); 13C NMR δ 148.8, 147.2,
144.7, 143.2, 137.4, 135.6, 127.9, 122.5, 120.8, 119.1, 111.1, 110.9,
55.7, 55.1, 50.1, 35.7, 31.5, 15.2; MS m/e 300.0 (M+, 100), 253
(43.9), 162 (41.3). Anal. Calcd for C18H20O2S (300.43): C, 71.96;
H, 6.71. Found: C, 72.13; H, 6.96.
1-(4-Meth oxyph en yl)-4-m eth yl-7-(m eth ylth io)in dan e (10a).
Yield 61% (0.59 g). Colorless oil: Rf ) 0.4 (1:9; ethyl acetate:
hexane); IR (neat) 2949, 1509, 1458, 1437 cm-1; 1H NMR δ 7.05
(d, J ) 8.3 Hz, 1H), 6.94 (br d, J ) 8.8 Hz, 3H), 6.78 (d, J ) 8.8
Hz, 2H), 4.44 (dd, J ) 9.0, 2.7 Hz, 1H,), 3.74 (s, 3H), 2.97 (ddd,
J ) 16.1, 8.3, 8.5 Hz, 1H), 2.89 (ddd, J ) 15.9, 9.4, 3.2 Hz, 1H),
2.58 (ddt, J ) 15.9, 9.4, 3.2 Hz, 1H), 2.28 (s, 3H), 2.26 (s, 3H),
2.0 (ddt, J ) 17.1, 8.6, 8.0 Hz, 1H);); 13C NMR δ 157.8, 143.8,
143.6, 137.4, 132.1, 130.5, 128.7, 128.4, 123.8, 113.7, 55.1, 50.0,
35.3, 30.3, 18.9, 15.7; MS m/e 285 (M+, 100), 270 (94), 237(46).
Anal. Calcd for C18H20OS (284.43): C, 76.01; H, 7.08. Found:
C, 76.18; H, 7.14.
S-Meth yl 2-(Bu t-1-en e-3-yl)-5-(4-m eth oxyp h en yl)cyclo-
p en t-2-en -1-ca r both ioa te (11a ). Yield 65% (0.67 g). Colorless
oil: Rf ) 0.55 (1:9; ethyl acetate:hexane); IR (neat) 2927, 1680,
1581, 1512, 1447 cm-1; 1H NMR δ 7.13-7.09 (m, 2H), 6.82 (dd,
J ) 8.8, 2.7 Hz, 2H), 5.93-5.59 (m, 2H), 5.06-4.95 (m, 2H), 3.77
(s, 3H), 3.75 (br s, 1H), 3.63-3.55 (m, 1H), 3.03-2.89 (m, 2H),
2.42 (br d, J ) 14.2 Hz, 1H), 2.29 (s, 3H), 1.23 (dd, J ) 6.8, 3.3
Hz, 3H); 13C NMR δ 201.9, 158.2, 144.6, 141.3, 137.8, 127.7,
126.9, 114.4, 113.9, 69.4, 55.2, 48.4, 41.0, 38.3, 18.8, 11.7; MS
m/e 302 (M+, 35.7), 226 (100). Anal. Calcd for C18H22O2S
(302.44): C, 71.49; H, 7.33. Found: C, 71.62; H, 7.16.
1-(4-Meth oxyph en yl)-4-m eth yl-5-(m eth ylth io)in dan e (16a).
Yield 65% (0.63 g). Colorless crystals (pentane): mp 64-65 °C;
Rf ) 0.5 (1:9 ethyl acetate:hexane); IR (KBr) 2998, 1609, 1511,
1454 cm-1; 1H NMR δ 7.0 (dd, J ) 8.8, 1.9 Hz, 2H), 6.92 (d, J )
7.8 Hz, 1H), 6.75 (dd, J ) 8.4, 1.9 Hz, 2H), 6.67 (d, J ) 7.8 Hz,
1H), 4.17 (d, J ) 8.3 Hz, 1H), 3.68 (s, 3H), 2.90 ((ddd, J ) 15.8,
9.1, 3.2 Hz, 1H), 2.74 (ddd, J ) 16.1, 8.3, 8.5 Hz, 1H), 2.45 (ddt,
J ) 12.7, 10.0, 6.3 Hz, 1H)), 2.32 (s, 3H), 2.24 (s, 3H), 1.9 (ddt,
J ) 13.0, 9.6, 6.3 Hz, 1H); 13C NMR δ 158.1, 144.3, 143.8, 137.6,
135.2, 132.1, 129.0, 124.7, 122.7, 113.8, 55.2, 50.9, 36.3, 30.8,
16.5, 16.4; MS m/e 284 (M+, 100), 237 (63). Anal. Calcd for
Rea ction Con d ition s B. To a solution of crude carbinol
(4a ,b, 5a , 13a , 14a ) obtained from an earlier reaction mixture
in dry benzene (25 mL) was added BF3‚Et2O (5 mmol, 0.65 mL)
at room temperature, and the reaction mixture was refluxed for
3 h (for carbinols 4a ,b, 5a ) or 5 h (13a ) or 15 h (for 14a )
(monitored by TLC). The reaction mixture was cooled to room
temperature, poured into an ice-cooled bicarbonate solution (15
mL), and extracted with ethyl acetate (3 × 30 mL). The organic
extracts were combined, washed with water, and dried over
anhydrous Na2SO4. The solvent was removed under reduced
pressure to afford substituted arylindane, which was purified
by column chromatography on silica gel using hexanes-ethyl
acetate (97:3) as eluent to obtain analytically pure product.
1-(4-Meth oxyph en yl)-5-m eth yl-7-(m eth ylth io)in dan e (6a).
Yield17 79% (0.76 g). Colorless needles (ether): mp 78-79 °C; Rf
) 0.7 (3:17; ethyl acetate:hexane); IR (KBr) 2910, 1580, 1550,
1425 cm-1 1H NMR δ 6.93 (dd, J ) 6.8, 2.2 Hz, 2H), 6.90 (s,
;
1H), 6.79 (s, 1H), 6.77 (dd, J ) 6.8, 2.2 Hz, 2H), 4.37 (dd, J )
8.8, 2.7 Hz, 1H), 3.74 (s, 3H), 3.04 (ddd, J ) 15.9, 8.3, 8.8 Hz,
1H), 2.83 (ddd, J ) 15.9, 9.4, 3.2 Hz, 1H), 2.53 (ddt, J ) 18.0,
10.9, 7.1 Hz, 1H), 2.37 (s, 3H), 2.31 (s, 3H), 1.97 (ddt, J ) 18.1,
8.8, 8.0 Hz, 1H); 13C NMR δ 157.8, 144.9, 140.7, 137.6, 137.3,
135.0, 128.4, 123.3, 121.7, 113.7, 55.1, 49.2, 36.1, 31.4, 21.4, 15.1;
MS m/e 285 (M+, 100), 270 (94), 237 (46). Anal. Calcd for C18H20
-
OS (284.43): C, 76.0; H, 7.08. Found: C, 76.22; H 7.19.
1-(2-Meth oxyph en yl)-5-m eth yl-7-(m eth ylth io)in dan e (6b).
Yield 75% (0.73 g). Colorless oil: Rf ) 0.7 (3:17; ethyl acetate:
hexane); IR (neat) 2954, 1596, 1564, 1489, 1457 cm-1; 1H NMR
δ 7.18-7.14 (m, 1H), 6.91 (s, 1H), 6.89 (d, J ) 8.3 Hz, 1H), 6.82
(s, 1H), 6.76-6.72 (m, 1H), 6.52 (d, J ) 8.8 Hz, 1H), 4.76 (d, J
) 8.8 Hz, 1H), 3.89 (s, 3H), 2.95 (ddd, J ) 16.1, 8.2, 8.8 Hz, 1H),
2.79 (ddd, J ) 15.7, 8.8, 2.4 Hz, 1H), 2.50 (ddt, J ) 18.1, 10.3,
8.8 Hz, 1H), 2.37 (s, 3H), 2.28 (s, 3H), 1.94 (ddt, J ) 12.7, 8.3,
2.4 Hz, 1H); 13C NMR δ 156.9, 145.8, 140.2, 137.4, 134.9, 132.7,
127.2, 127.1, 123.2, 121.6, 120.2, 110.4, 55.5, 43.0, 34.3, 31.3,
21.5, 15.2; MS m/e 284 (M+, 68.7), 269 (37.7), 237 (100). Anal.
Calcd for C18H20OS (284.43): C, 76.0; H, 7.08. Found: C, 76.29;
H, 7.21.
3-[3-(Met h ylt h io)-3-p h en ylp r op yl]-5-(m et h ylt h io)t olu -
en e (7). Yield 62% (0.64 g). Yellow oil: Rf ) 0.7 (1:10; ethyl
acetate:hexane); IR (neat) 2916, 1579, 1490, 1449 cm-1; 1H NMR
δ 7.26-7.13 (m, 5H), 6.80 (s, 1H), 6.74 (s, 1H), 6.63 (s, 1H), 3.54
(t, J ) 6.8 Hz, 1H), 2.47 (t, J ) 6.8 Hz, 2H), 2.35 (s, 3H), 2.19 (s,
3H), 2.14-2.0 (m, 2H); 1.75 (s, 3H); 13C NMR δ 142.0, 141.9,
138.4, 138.0, 128.4, 127.8, 127.0, 126.1, 124.7, 123.6, 50.6, 37.2,
33.5, 21.2, 15.7, 14.1; MS m/e 302 (M+, 43.8), 253 (35.8), 151
(100). Anal. Calcd for C18H22S2 (302.50): C, 71.47; H, 7.33.
Found: C, 71.59; H, 7.18.
1-(4-Meth oxyp h en yl)-7-(m eth ylth io)In d a n e (9a ). Yield
65% (0.60 g). Colorless crystals (ether): mp 68-69 °C; Rf ) 0.65
(3:17; ethyl acetate:hexane); IR (KBr) 2949, 1512, 1454, 1438
cm-1; 1H NMR δ 7.26-7.21 (m, 1H), 7.11 (d, J ) 7.4 Hz, 1H), 7.
01 (d, J ) 7.8 Hz, 1H), 6.97 (dd, J ) 8.8, 3.6 Hz, 2H), 6.81(dd,
J ) 8.8, 3.2 Hz, 2H), 4.42 (d, J ) 9.0 Hz, 1H), 3.78 (s, 3H), 3.11
(ddd, J ) 16.01, 8.4, 8.8 Hz, 1H), 2.90 (ddd, J ) 15.8, 8.8, 2.2
Hz, 1H), 2.59 (ddt, J ) 15.3, 10.4, 9.0 Hz), 2.33 (s, 3H), 2.0 (ddt,
J ) 16.3, 9.4, 2.9 Hz, 1H); 13C NMR δ 157.8, 144.7, 143.5, 137.0,
135.5, 128.4, 127.8, 122.4, 120.8, 113.7, 55.1, 49.6, 35.8, 31.5,
15.1; MS m/e 270 (M+, 100), 255 (85). Anal. Calcd for C17H18OS
(270.40): C, 75.51; H, 6.71. Found: C, 75.68; H, 6.97.
C
18H20OS (284.43): C, 76.01; H, 7.09. Found: C, 76.21; H, 7.18.
4,7-Dim e t h yl-1-(4-m e t h oxyp h e n yl)-5-(m e t h ylt h io)in -
d a n e (17a ). Yield 61% (0.62 g). Colorless oil: Rf ) 0.45 (1:9; ethyl
acetate:hexane); IR (neat) 2919, 1510, 1458, 1437 cm-1; 1H NMR
δ 6.93 (dd, J ) 6.6, 2.0 Hz, 2H), 6.85 (s, 1H), 6.78 (dd, J ) 6.6,
2.0 Hz, 2H), 4.34 (dd, J ) 8.8, 1.6 Hz, 1H), 3.77 (s, 3H), 3.93 (m,
1H), 2.86-2.79 (m, 1H), 2.53 (m, 1H), 2.45 (s, 3H), 2.31 (s, 3H),
2.94 (ddt, J ) 12.7, 10.3, 6.6 Hz, 1H)), 1.92 (s, 3H); 13C NMR δ
157.8, 143.9, 141.9, 138.0, 132.5, 129.5, 128.3, 127.5, 126.2, 113.8,
55.2, 49.6, 35.7, 30.7, 18.9, 16.4, 16.2; MS m/e 298 (M+, 100),
250 (56.3). Anal. Calcd for C19H22OS (298.45): C, 76.47; H, 7.43.
Found: C, 76.34; H, 7.29.
Eth yl 2-{[Bis(m eth ylth io)m eth ylen e]a cetyl}-3-(4-m eth -
oxyp h en yl)cyclop r op a n eca r boxyla te (25a ). To a well-stirred
solution of ethyl (dimethylsulfuranylidine)acetate (EDSA)15 (15
mmol) in chloroform (50 mL) at 0 °C was injected cinnamoyl
ketenedithioacetal 24a (2.8 g, 10 mmol) in chloroform (20 mL),
and the reaction mixture was stirred at room temperature for
(2 h) and then refluxed for 30 h (monitored by TLC). It was then
cooled and concentrated under reduced pressure to afford crude
25a , which was purified by being passes through a silica gel
column using hexanes-ethyl acetate (24:1) as eluent. Yellow oil:
yield 71% (2.6 g); Rf ) 0.5 (1:4; ethyl acetate:hexane); IR (neat)
1
2980, 1729, 1695, 1512, 1302, 1249 cm-1; H NMR δ 7.10 (d, J
) 8.3 Hz, 2H), 6.73 (d, J ) 8.3 Hz, 2H), 6.25 (s, 1H), 3.94-3.86
(q, J ) 7.0 Hz, 2H), 3.70 (s, 3H), 3.04-3.01 (m, 1H), 2.93-2.90
(m, 1H), 2.58-2.56 (m, 1H), 2.45 (s, 3H), 2.43 (s, 3H), 1.01 (t, J
) 7.0 Hz, 3H); 13C NMR δ 190.2, 169.3, 165.5, 158.5, 130.0, 127.1,
113.5, 112.4, 60.6, 55.1, 34.0, 33.7, 31.6, 17.2, 14.9, 14.1; MS m/e
366 (M+, 25.5), 293 (49), 147 (100). Anal. Calcd for C18H22O4S2
(366.50): C, 58.99; H, 6.05. Found: C, 59.11; H, 6.27.
1-(3,4-Dim eth oxyph en yl)-7-(m eth ylth io)in dan e (9b). Yield
69% (0.7 g). Viscous liquid: Rf ) 0.6 (3:17; ethyl acetate:hexane);
IR (neat) 2984, 1589, 1573, 1441 cm-1 1H NMR δ 7.27-7.22
;
(m, 1H), 7.12 (d, J ) 7.6 Hz, 1H), 7.02 (d, J ) 7.6 Hz, 1H), 6.75
(d, J ) 8.3 Hz, 1H), 6.65 (d, J ) 2.0 Hz, 1H), 6.52 (dd, J ) 8.0,
1.9 Hz, 1H), 4.42 (dd, J ) 9.0, 2.9 Hz, 1H), 3.88 (s, 3H), 3.82 (s,
3H), 3.12 (ddd, J ) 15.9, 8.3, 8.7 Hz, 1H), 2.9 (ddd, J ) 15.9,
9.4, 3.2 Hz, 1H), 2.60 ((ddt, J ) 17.8, 10.8, 7.0 Hz, 1H), 2.34 (s,
Gen er a l P r oced u r e for th e Ad d ition of Allylic In d iu m
Rea gen ts to 2-Ca r boeth oxycyclop r op yl Keton e (25a ). To
a suspension of indium powder (0.68 g) in dry DMF (5 mL) was
injected allyl bromide (or methallyl bromide) (9.0 mmol) through
a septum, and the reaction mixture was stirred for 1 h at room
temperature. A solution of 25a (3 mmol) in dry DMF (3 mL)
was added, and the stirring was continued for 24-30 h (moni-
(17) The reported yields of all substituted arylindanes are the overall
yields from their respective cyclopropyl ketones.