3914
S. Hirano et al. / Tetrahedron 62 (2006) 3896–3916
7
1
1
1
3.02 (2 peaks), 74.73, 117.83, 127.14, 127.21, 127.52,
yellow homogeneous solution. The solution was warmed to
K50 8C over 30 min, during which period its color turned
red. After stirring at K50 8C for 3 h, the reaction was
28.00, 128.12, 128.36, 128.46, 129.52, 133.73, 134.65,
34.71, 138.71, 144.21; IR (neat) 3041, 2919, 2860, 2250,
496, 1453, 1364, 1169, 1092, 1034, 928, 854, 813, 756,
terminated by the addition of H O (0.10 mL) and the
2
K1
6
Found: C, 74.83; H, 6.51.
98 cm . Anal. Calcd for C H NO S: C, 74.84; H, 6.62.
4
heterogeneous mixture was filtered through Celite with the
aid of ether. The organic phase was concentrated in vacuo to
give a crude oil, H NMR analysis of which showed the
3
7
39
1
4.1.66. N-[4,4-Bis(benzyloxymethyl)-6-hepten-1-yn-1-
yl]-3-(tert-butyl)-1,2-benzisothiazoline 1,1-dioxide (74).
H NMR d 1.10 (s, 9H), 2.28 (d, JZ7.5 Hz, 2H), 2.47 (s,
diastereoselectivity to be 1:1. The crude product was
chromatographed on silica gel (hexane–ethyl acetate) to
afford the title compound (53 mg, 87%) as a colorless oil.
1
1
2
9
7
2
H), 3.44 (s, 4H), 4.39 (s, 1H), 4.53 (s, 4H), 5.07 (d, JZ
.9 Hz, 1H), 5.13 (d, JZ17.4 Hz, 1H), 5.75–5.89 (m, 1H),
.25–7.34 (m, 10H), 7.47 (d, JZ7.5 Hz, 1H), 7.54–7.65 (m,
H NMR d 1.15–1.21 (m, 4H), 1.43 (d, JZ6.6 Hz, 1.5H)
1.45 (d, JZ6.6 Hz, 1.5H), 2.04 (d/d, JZ10.2, 13.8 Hz, 1H),
2.58 (br s, 2H), 2.77 (m, 1H), 3.35–3.43 (m, 4H), 4.46–4.51
(m, 5H), 5.55 (q, JZ2.4 Hz, 0.5H), 5.64 (q, JZ2.4 Hz,
0.5H), 7.26–7.33 (m, 10H), 7.37 (d, JZ7.5 Hz, 1H), 7.52 (t,
JZ7.5 Hz, 1H), 7.62 (t, JZ7.5 Hz, 1H), 7.80 (d, JZ7.5 Hz,
1H). Irradiation of proton at d 5.55–5.64 ppm (vinylic H)
showed 3% NOE enhancement to the peak at d 2.77 ppm
(C]CCHMe). Irradiation of proton at d 2.77 ppm
(C]CCHMe) showed 3% NOE enhancement to the peak
at d 5.55–5.64 ppm (vinylic H). Thus, the stereochemistry
1
3
H), 7.82 (d, JZ6.6 Hz, 1H); C NMR d 22.36, 26.77 (t-
Bu), 36.30, 38.16, 42.50, 69.45, 71.98 (2 peaks), 72.92,
7
1
1
1
3.22 (2 peaks), 75.19, 118.11, 121.89, 125.79, 127.34,
27.45 (2 peaks), 128.27, 129.53, 132.54, 134.03, 135.57,
38.95; IR (neat) 3082, 3025, 2960, 2919, 2862, 2250, 1466,
K1
328, 1254, 1181, 1115, 1091, 936, 736, 707 cm . Anal.
Calcd for C H NO S: C, 73.22; H, 7.05. Found: C, 73.09;
4
3
4
39
H, 6.87.
1
3
has been confirmed. C NMR d 17.74, 18.55, 18.64, 19.87,
36.21, 36.74, 39.95, 40.36, 45.71, 46.25, 58.17, 58.33,
72.84, 73.22, 73.38, 74.65, 74.82, 77.21, 111.52, 111.99,
121.51, 123.63, 123.67, 127.41, 127.49, 127.52, 127.55,
128.28, 128.32, 128.35, 129.10, 132.89, 132.95, 134.72,
138.90, 139.16, 157.28, 157.84. (Peaks of diastereoisomers
may be overlapping.) IR (neat) 3025, 2960, 2927, 2856,
1496, 1453, 1363, 1304, 1279, 1172, 1148, 1099, 1034, 910,
4.1.67. (R)-N-(p-Toluenesulfonyl)-N-[4,4-bis(benzyloxy-
methyl)-6-hepten-1-yn-1-yl]-N-(2-methoxy-1-phenyl-
ethyl)amine (75). H NMR d 1.99 (d, JZ7.8 Hz, 2H), 2.35
1
(
s, 3H), 2.38 (s, 2H), 3.22 (s, 3H), 3.33 (s, 4H), 3.60 (d/d,
JZ4.8, 9.9 Hz, 1H), 3.80 (t, JZ9.9 Hz, 1H), 4.44 (s, 4H),
5
7
8
6
1
1
.01 (m, 2H), 5.21 (d/d, JZ4.8, 9.9 Hz, 1H), 5.73 (m, 1H),
.11 (d, JZ8.4 Hz, 2H), 7.22–7.34 (m, 15H), 7.64 (d, JZ
1
3
K1
.4 Hz, 2H); C NMR d 21.44, 22.34, 36.20, 42.54, 58.65,
1.58, 70.04, 72.02 (2 peaks), 72.30, 72.39, 73.24 (2 peaks),
18.05, 127.36, 127.39, 127.44, 128.00, 128.27, 128.35,
28.54, 129.16, 134.00, 135.76, 136.72, 138.91, 143.91; IR
735, 699 cm for a 1:1 mixture of diastereoisomers. Anal.
Calcd for C31H35NO S: C, 71.92; H, 6.81. Found: C, 71.64;
4
H, 6.56 for a 1:1 mixture of diastereoisomers.
(
neat) 3066, 3025, 2927, 2861, 2258, 1597, 1491, 1453,
363, 1181, 1092, 1034, 958, 928, 813, 748, 701 cm
4.1.70. N-Benzyl-N-[[(E)-4,4-bis(benzyloxymethyl)-2-
methyl-1-cyclopentylidene]methyl]-p-toluenesulfona-
mide (77). H NMR d 0.96 (d, JZ6.0 Hz, 3H), 1.22–1.36
(m, 1H), 1.82–1.92 (m, 1H), 2.18 (s, 2H), 2.44 (s, 3H), 2.40–
K1
1
.
Anal. Calcd for C H NO S: C, 73.44; H, 6.80. Found: C,
1
3
9
2
43
5
8
7
3.18; H, 6.57; [a] C51.2 (c 3.36, CHCl3).
D
2
4.32–4.50 (m, 4H), 4.97–5.05 (m, 1H), 7.16–7.40 (m, 17H),
7.70 (d, JZ8.1 Hz, 2H); C NMR d 19.19, 21.51, 35.50,
.54 (m, 1H), 2.99–3.14 (m, 4H), 4.18 (d, JZ3.9 Hz, 2H),
4
.1.68. (1S,2S)-N-[4,4-Bis(benzyloxymethyl)-6-hepten-1-
yn-yl]-2,10-camphorsultam (76). H NMR d 0.99 (s, 3H),
1
13
1
.09 (s, 3H), 1.28–1.31 (m, 1H), 1.38–1.44 (m, 1H), 1.64 (d/
d, JZ5.1, 8.1 Hz, 1H), 1.85–1.92 (m, 3H), 2.05–2.15 (m,
H), 2.24 (d, JZ7.5 Hz, 2H), 2.40 (s, 2H), 3.21 (s, 2H), 3.41
s, 4H), 3.46 (t, JZ7.8 Hz, 1H), 4.51 (s, 4H), 5.05 (d, JZ
0.4 Hz, 1H), 5.10 (d, JZ17.4 Hz, 1H), 5.72–5.86 (m, 1H),
37.00, 39.67, 45.73, 54.44, 72.48, 73.03 (2 peaks), 74.46,
117.36, 127.25, 127.50, 128.18, 129.05, 129.50, 135.20,
136.09, 138.89, 143.27, 155.85. Peaks of aromatic carbons
1
(
may be overlapping. IR (neat) 3029, 2968, 2927, 2855,
1598, 1496, 1453, 1355, 1165, 1099, 815, 739, 697 cm
K1
1
7
3
6
1
3
1
.
1
3
.24–7.36 (m, 10H); C NMR d 19.79, 20.04, 22.24, 26.87,
1.44, 34.28, 36.30, 42.31, 44.27, 47.78, 49.44, 50.80,
7.04, 69.28, 69.37, 71.99 (2 peaks), 73.25 (2 peaks),
18.11, 127.35, 127.43, 128.28, 133.96, 138.94; IR (neat)
066, 2959, 2895, 2854, 2250, 1638, 1453, 1338, 1320,
Anal. Calcd for C37H41NO S: C, 74.59; H, 6.94. Found: C,
4
74.75; H, 6.93.
4.1.71. N-[[(E)-4,4-Bis(benzyloxymethyl)-2-methyl-1-
cyclopentylidene]methyl]-3-(tert-butyl)-1,2-benzisothia-
zoline 1,1-dioxide as a 1:1 mixture of diastereoisomers
K1
270, 1140, 1095, 919, 737, 699 cm . Anal. Calcd for
1
C H NO S: C, 72.36; H, 7.54. Found: C, 72.51; H, 7.59;
4
(79). H NMR d 1.04 (s, 9H), 1.08 (d, JZ6.6 Hz, 1.5H) 1.15
3
3
2
41
8
[
a] C8.3 (c 0.936, CHCl3).
(d, JZ6.6 Hz, 1.5H), 1,25–1,29 (m, 1H), 1.97–2.08 (m, 1H),
D
2.51–2.63 (m, 1H), 2.65–2.85 (m, 2H), 3.29–3.59 (m, 4H),
4.12 (s, 0.5H), 4.17 (s, 0.5H), 4.42–4.62 (m, 4H), 5.31 (d,
4
.1.69. Typical procedure for Scheme 9. N-[[(E)-4,4-
Bis(benzyloxymethyl)-2-methyl-1-cyclopentylidene]-
methyl]-3-methyl-1,2-benzisothiazoline 1,1-dioxide as a
JZ1.8 Hz, 0.5H), 5.44 (d, JZ1.8 Hz, 0.5H), 7.24–7.36 (m,
1
3
10H), 7.43–7.58 (m, 3H), 7.76–7.82 (m, 1H). C NMR d
17.10, 21.95, 27.13, 29.66, 35.82, 35.86, 37.00, 37.11,
38.06, 38.24, 39.69, 40.53, 45.98, 47.33, 72.19, 73.08,
73.19, 73.75, 7452, 74.79, 75.13, 75.38, 119.13, 120.45,
121.62, 121.65, 125.51, 127.20, 127.26, 127.41, 127.45,
128.15, 128.21, 128.94, 128.97, 131.75, 131.79, 136.19,
136.88, 136.97, 138.83, 147.25, 148.35. (Peaks of
1
:1 mixture of diastereoisomers (78). To a stirred solution
of N-[4,4-bis(benzyloxymethyl)-6-hepten-1-yn-1-yl]-3-
methyl-1,2-benzisothiazoline 1,1-dioxide (73) (47 mg,
0
1
0
.097 mmol) and Ti(O–i-Pr) (0.057 mL, 0.193 mmol) in
4
.0 mL of Et O was added i-PrMgCl (1.50 M in Et O,
2
2
.257 mL, 0.386 mmol) at K78 8C under argon to give a