Tandem Ring Closure-SRN1 Reactions
3-(Dip h en yl-p h osp h in oylm eth yl)-2,3-d ih yd r o-ben zofu -
r a n (7b): white solid, mp 123-124 °C, purified by column
chromatography with a 50/50 hexane/ethyl acetate mixture
0.74, 6.9); 7.06 (1 H, br d, J ) 7.3). 13C NMR (CD3COCD3) δc:
-9.61; 17.16; 40.76; 56.53; 109.42; 118.08; 123.71; 127.58;
135.69; 152.51. δc DEPT 135: (CH2) 17.16; 56.58. CH: 40.76;
109.41; 118.09; 123.75; 127.58. GC/MS EI, m/z (%): 41 (6), 77
(17), 91 (9), 106 (15), 117 (isotopic cluster, 15), 130 (100), 132
(98), 208 (isotopic cluster, 6), 224 (isotopic cluster, 12), 250
(isotopic cluster, 25), 280 (isotopic cluster, 42), 297 (M+, isotopic
cluster, 5). DEI-HRMS calcd for C12H19N120Sn, 297.0539; found
297.0537.
1
as the solvent. H NMR (CDCl3) δH: 2.56 (d t, 1 H, J ) 10.6,
15); 2.77 (q d, 1H, J ) 3.3, J ) 9.5, 10.2); 3.83 (br m, 1 H);
4.27 (dd, 1 H, J ) 9.1, 9.5); 4.56 (t, 1 H, J ) 8.8, 9.5); 6.80
(octet, 2 H); 7.11 (cplx. t, 2 H); 7.52 (br cplx. m, 6 H); 7.78 (br
cplx. m, 4 H). 13C NMR (CDCl3) δc: 35.40 (d, P-CJ ) 69); 36.28
(d, J ) 4); 109,77; 120.61; 123.92; 128.67; 128.73; 128.77;
128.94; 130.58; 130.71; 130.90; 132.01; 132.06; 159.55. GC/MS
EI, m/z (%): 47 (21), 65 (9), 77 (38), 91 (19), 125 (19), 131 (19),
155 (28), 183 (9), 202 (88), 215 (100), 216 (60), 317 (0.5), 334
(12). DEI-HRMS calcd for C21H19O2P, 334.1123; found, 334.1119.
1-(3-Tr im et h ylst a n n a n ylm et h yl-2,3-d ih yd r o-in d ol-1-
yl)-eth a n on e (9a ): white solid, mp 73-74 °C, obtained in 97%
yield by column chromatography with a 75/25 hexane/dichlo-
romethane mixture. 1H NMR (CDCl3) δH: 0.04 (ss, 9 H, CH -SnJ
3
) 26.4, 1.1); 1.28 (cplx. m, 2 H, J ) 8.4, 4.4); 2.20 (s s, 3 H);
3.49 (cplx. m, 1 H); 3.71 (br cplx. m, 1 H); 4.18 (br t, 1 H, J )
9.5); 7.02 (d t, 2 H, J ) 1.1, 7.7); 7.15 (d q, 2 H, J ) 1.1, 8.4);
3-(2-Nitr o-eth yl)-2,3-d ih yd r oben zofu r a n (7c): obtained
as a colorless liquid, purified by radial thin-layer chromatog-
1
raphy with hexane. H NMR (CDCl3) δH: 2.44 (cplx. m, 2 H);
8.18 (b d, 2 H, J ) 8). 13C NMR (CDCl3) δc: -9.49 (H C-SnJ )
3
3.60 (br quintet, 1 H); 4.23 (q, 1 H, J ) 4.8, 9); 4.42 (t, 2 H, J
) 7.3); 4.60 (d t, 1 H); 6.91 (d, 1 H, J ) 8.1); 6.99 (d t, 1 H, J
) 7.7, 7.3); 7.27 (cplx. m, 2 H). 13C NMR (CDCl3) δc: 32.13;
38.94; 72.98; 75.84; 109.99; 120.80; 121.96; 128.29; 129.02;
159.69. GC/MS EI, m/z (%): 65 (27), 77 (9), 91 (100), 119 (35),
145 (16), 193 (12). DEI-HRMS calcd for C10H11NO3, 193.0739;
found, 193.0734.
163, 6.7); 18.35; 24.15; 38.38; 57.81; 116.97, 123.44; 123.74;
127.68; 137.40; 142.12; 168.43. GC/MS EI, m/z (%): 43 (91),
77 (24), 91 (13), 103 (16), 117 (39), 130 (89), 132 (79), 165 (25),
174 (100), 324 (isotopic cluster, 37), 339 (2). DEI-HRMS: calcd
for C13H18NO120Sn (M+ -15), 324.0410; found, 324.0416.
1-[3-(Dip h en yl-p h osp h in oylm eth yl)-2,3-d ih yd r o-in d ol-
1-yl]-eth a n on e (9b): white solid, mp 102-104 °C, purified
by recrystallization in a ca. 80/20 hexane/acetone mixture.
1H NMR (CDCl3) δH: 2.11 (ss, 3 H); 2.55 (sextet, 1 H); 2.77
(dq, 1 H, J ) 3, J ) 9, J ) 12); 3.74 (br cplx. m, 1 H); 3.95 (dd,
1 H, J ) 5.5); 4.15 (cplx. t, 1 H); 7.10 (cplx. m, 3 H), 7.52 (br
cplx. m, 7 H); 7.78 (cplx. m, 3 H), 8.16 (b d, 1 H, J ) 8). 13C
NMR (CDCl3) δc: 24.09; 34.82; 35.67 (d, J ) 70); 54.95; 117.16;
123.28; 123.74; 128.45; 128.80; 128.91; 129.04; 129.15; 130.47;
130.72; 130.90; 132.20; 142.33; 168.96. GC/MS EI, m/z (%): 47
(12), 77 (14), 91 (7), 130 (33), 174 (6), 202 (10), 215 (100), 216
(61), 375 (3). DEI-HRMS calcd for C23H22NO2P, 375.1388,
found, 375.1385.
1-Allyl-3-t r im et h ylst a n n a n ylm et h yl-2,3-d ih yd r o-1H -
in d ole (8a ): colorless liquid obtained in 97% yield by column
chromatography with hexane. 1H NMR (CD3COCD3) δH: 0.067
(s s, 9H, CH -SnJ ) 13); 1.02-0.89 (cplx. m, 1 H); 1.20 (cplx. m,
3
1 H, J ) 1.1, 7); 1.33 (br s, 1 H); 1.46 (t d, 1 H, J ) 2.6, 4.4,);
2.95-2.78 (cplx. m, 1 H); 3.56 (cplx. m, 2 H); 3.74 (q t, 2 H, J
) 1.46, 6.2); 3.75 (q t, 1 H, J ) 1.1, 6.2, 13.9); 5.21 (cplx. d
quintet, 1 H, J ) 1.46, 3.6,10.2); 5.32 (d q, 1 H, J ) 1.46, 3.3,
17.1); 5.96 (q t, 1 H, J ) 5.8, 6.2, 10.2, 17.1), 6.54 (d, 1 H,
J ) 7.7); 6.65 (d t, J ) 1.1, 7.7); 7.03 (br t, 2 H). 13C NMR
(CD3COCD3) δc: -9.23 (t, J ) 161); 17.29; 39.57; 52.41; 62.61;
108.20; 117.49; 118.49; 123.97; 128.05; 135.33; 137.21; 152.51.
GC/MS EI, m/z (%): 77 (15), 91 (88), 103 (9), 117 (9), 130 (81),
131 (11), 170 (100), 172 (38), 320 (isotopic cluster, 21), 337
(1,2-Dih yd r o-n a p h t h o[2,1-b]fu r a n -1-ylm e t h yl)-t r i-
m eth yl-sta n n a n e (10a ): colorless oil purified by radial thin-
layer chromatography with hexane. 1H NMR (CDCl3) δH: -0.09
(s s, 9 H, H-SnJ ) 26); 1.28-1.6 (cplx. m, 2 H); 4.21 (cplx. m, 2
H); 4.75 (b t, 1 H, J ) 8.8): 7.08 (d, 1 H, J ) 8.8); 7.29 (br d,
1 H); 7.44 (br t, 1 H, J ) 6.9); 7.71 (sextet, 3H). 13C NMR
(CDCl3) δc: -9.87; 18.19; 39.62; 79.53; 112.20; 122.23; 122.58;
124.60; 126.43; 128.91; 129.61; 130.34; 156.56. GC/MS EI, m/z
(%): 51 (6), 63 (8), 77 (9), 115 (23), 135 (cluster, 14), 141
(cluster, 27), 152 (cluster, 42), 165 (60), 183 (cluster, 100), 333
(isotopic cluster, 3). DEI-HRMS calcd for C14H20N120Sn (M+
15), 322.0618; found, 322.0624.
-
1-Allyl-3-(d ip h en yl-p h osp h in oylm et h yl)-2,3-d ih yd r o-
1H-in d ole (8b): obtained as an off-white oil, purified by
column chromatography with a 50/50 hexane/ethyl acetate
1
mixture. H NMR (CDCl3) δH: 2.70 (cplx. m, 2 H); 3.13 (cplx.
m, 1 H); 3.43-3.82 (cplx. m, 3 H); 5.12 (cplx. d, 1 H, J ) 1.1,
9.8); 5.23 (cplx. t, 1 H, J ) 1.4, 3); 6.1-5.71 (cplx. m, 2 H);
6.48 (d, 1 H, J ) 7.7); 6.64 (t, 1 H, J ) 7.3); 7.05 (cplx. m, 2
H); 7.50 (br cplx. m, 6 H); 7.78 (br cplx. m, 4 H). 13C NMR
(CDCl3) δc: 34.86 (d, J ) 70); 51.56; 59.50 (d, J ) 3); 64.2;
107.56; 113.57; 117.51; 117.55; 123.22; 127.99; 128.56; 128.64;
128.78; 128.88; 130.53; 130.72; 130.90; 131.79; 133.60; 151.50.
GC/MS EI, m/z (%): 65 (3), 77 (21), 91 (10), 130 (27), 170 (55),
171 (62), 183 (6), 201 (7), 215 (100), 216 (39), 277 (9), 373 (7).
DEI-HRMS calcd for C24H24NOP, 373.1596; found, 373.1599.
(cluster, 38), 349 (cluster, 4). DEI-HRMS calcd for C16H20O120
Sn, 348.0536; found, 348.0534.
-
1-(Diph en yl-ph osph in oylm eth yl)-1,2-dih ydr o-n aph th o-
[2,1-b]fu r a n (10b): white solid, mp 156-158 °C, obtained in
97% yield by recrystallization in a ca. 80/20 hexane/acetone
mixture. 1H NMR (CDCl3) δH: 2.70 (13 lines, 2 H); 4.14 (br
cplx. m, 1 H); 4.58 (t, 1 H, J ) 8.4); 4.73 (dd, 1 H, J ) 2.6,
9.5); 7.09 (d, 1 H, J ) 8.8); 7.93-7.29 (cplx. m, 15 H). 13C NMR
(CDCl3) δc: 35.10 (d, C-PJ ) 69); 36.26 (d, J ) 4); 76.87 (d, J
) 3); 109.75; 120.61; 123.90; 128.64; 128.68; 128.75; 128.93;
128.98; 130.54; 130.70; 130.73; 130.88; 132.01; 132.04; 159.55.
GC/MS EI, m/z (%): 47 (14), 77 (12), 115 (15), 152 (19), 182
(100), 202 (28), 215 (47), 384 (14). DEI-HRMS calcd for
1-Allyl-3-(2-n it r o-et h yl)-2,3-d ih yd r o-1-H -in d ole (8c):
slightly yellow oil, purified by radial thin-layer chromatogra-
1
phy with hexane. H NMR (CDCl3) δH: 2.37 (d sextet, 2 H, J
) 6.9, 7.3, 14, 23), 3.11 (q, 1 H, J ) 4.7, 8.7); 3.31 (br q, 1 H);
3.50 (s t, 1 H, J ) 8.4), 3.72 (cplx. m, 2 H); 4.46 (d t, 2 H, J )
7.3, 9.1); 5.27 (d q, 1 H, J ) 1.4, 3.3), 5.26 (cplx. m, 1 H); 5.90
(quadrup. t, 1 H, J ) J ) 5.8, 10.2, 23); 6.55 (d, 1 H, J ) 8);
6.72 (d t, 1 H, J ) 0.7, 7); 7.13 (cplx. m, 2 H). 13C NMR (CDCl3)
δc: 31.67; 37.49; 51.61; 58.40; 73.36; 107.75; 117.56; 117.94;
123.92; 128.32; 131.04; 133.62; 151.60. GC/MS EI, m/z (%): 63
(2), 77 (1); 89 (4), 117 (63), 130 (53), 158 (100), 170 (2), 232
C
25H21O2P, 384.1279; found 384.1276.
1-(2-Nitr o-eth yl)-1,2-dih ydr o-n aph th o[2,1-b]fu r an (10c):
slightly yellow oil, purified by radial thin-layer chromatogra-
1
phy with hexane. H NMR (CDCl3) δH: 2.39 (10 lines, 1 H, J
) 6.2, 7.7); 2.61 (10 lines, 1 H, J ) 4.0, 14.6, 18.3); 3.94 (br
septet, 1 H); 4.41 (14 lines, 3 H); 4.71 (t, 1 H, J ) 9); 7.12 (d,
1 H, J ) 8.8); 7.34 (cplx. t, 1 H); 7.52 (cplx. t, 1 H); 7.75 (cplx.
m, 3 H). 13C NMR (CDCl3) δc: 31.05; 38.59; 72.93; 76.22;
112.17; 119.61; 121.79; 123.22; 127.29; 129.13; 129.64; 130.20;
130.29; 157.40. GC/MS EI, m/z (%): 63 (5), 89 (4), 115 (31),
141 (77), 169 (100), 181 (14), 196 (16), 243 (28). DEI-HRMS
calcd for C14H13NO3, 243.0895; found, 243.0903.
(40). DEI-HRMS calcd for
232.1205.
C13H16N2O2, 232.1212; found,
3-Tr im et h ylst a n n a n ylm et h yl-2,3-d ih yd r o-1H -in d ole
(8d ): slightly yellow oil, purified by radial thin-layer chroma-
tography with hexane and obtained in 30% yield. 1H NMR
(CD3COCD3) δH: 0.072 (ss, 9 H, Sn-HJ ) 1.46, 27); 150-1.43
(cplx. m, 2 H); 3.08 (br t, 1 H, J ) 6.9); 3.73-3.52 (cplx. m, 2
H); 4.74 (br s, 1 NH); 6.63 (cplx. q; 2 H); 6.95 (t t, 1H, J )
Ack n ow led gm en t. This work was supported in part
by the Agencia Co´rdoba Ciencia de la Provincia de
J . Org. Chem, Vol. 67, No. 24, 2002 8505