Sajna et al.
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6.43 (d, 2J(P-H)=15.6 Hz, 1H), 7.19-7.46 (m, 5H); 13C NMR
IR (neat, cm-1) 2967, 2888, 1734, 1647, 1445, 1254, 1075, 833,
783; 1H NMR (400 MHz, CDCl3) δ 0.67-1.10 (m, 23H), 1.63 (d,
3J(H-H)=4.0 Hz, 3H, isomer 38c), 1.77-1.86 (m, 2H, isomer
38d), 3.57-3.61 (m, 4H), 3.87, 3.88, 4.02, and 4.03 (4 s, 12H),
(100 MHz, CDCl3) δ 13.5, 14.0, 18.7, 21.3, 21.7, 32.5 (d, 3J(P-C)=
1
6.9 Hz), 44.9 (d, J(P-C)= 138.5 Hz), 61.8, 62.1, 75.9, 76.0,
125.6, 126.9, 128.0, 130.1 (d, 2J(P-C) = 8.9 Hz), 131.1 (d,
2J(P-C)=7.4 Hz), 133.5, 134.8, 135.2 (d, J(P-C)=5.4 Hz),
4.05-4.13 (m, 6H), 5.44-5.86 (m, 3H), 6.72 (dd, J(H-H)=
3
3
135.7 (d, 3J(P-C)=6.4 Hz), 166.2, 167.1; 31P NMR (162 MHz,
CDCl3) δ 17.2; LC/MS m/z 645 [M þ 1]þ. Anal. calcd for
C33H41O11P: C 61.48; H 6.41. Found: C 61.32; H 6.45. Isomeric
compounds 37(c,d): These compounds were separated by using
ethyl acetate/hexane (2:3) mixture as the eluent. Yield quanti-
tative [37aþ37bþ37(c,d)] by 31P NMR, 0.41 g (isolated, 42%,
37(c,d) ≈ 1:1); gummy; IR (neat, cm-1) 2978, 2942, 1730, 1470,
1372, 1258, 1059, 828, 785; 1H NMR (400 MHz, CDCl3) δ 0.71
and 0.73 (2 s, 6H), 0.87 (t, 3J(H-H)=8.0 Hz, 3H, isomer 37d),
1.29-1.47 (m, 18H), 1.62 and 1.64 (2 br s, 5H), 3.58-3.97 (m,
8H), 4.12 (s, 2H, isomer 37c), 4.29-4.50 (m, 8H), 5.45-5.85 (m,
11.8 Hz, 4J(P-H) ≈ 1.8 Hz, 1H, isomer 38d), 7.57-8.75 (m, 8H);
13C NMR (100 MHz, CDCl3) δ 6.8, 7.3, 13.4, 18.0, 22.0, 22.10,
22.14, 22.9, 35.6 (d, 3J(P-C) = 4.7 Hz), 37.1 and 37.2 (2 d,
3J(P-C)=5.7 and 5.0 Hz respectively), 52.7, 53.10, 53.13, 73.8,
74.0, 74.4 (d, 3J(P-C)=6.3 Hz), 125.4, 125.5 (d, 3J(P-C)=4.0
3
Hz), 126.1, 126.2, 126.8 (d, J(P-C) = 3.7 Hz), 127.1, 127.2,
127.6, 128.00, 128.02, 128.1, 128.2, 128.5, 128.8, 129.0, 131.6 (d,
2J(P-C)=16.8 Hz), 132.1 (d, 2J(P-C)=16.8 Hz), 133.6, 133.7,
133.8, 133.9, 134.0, 134.1, 134.9, 138.4, 138.8 (d, 2J(P-C)=11.0
Hz), 142.1 (d, 2J(P-C)=12.6 Hz), 167.6, 168.00, 168.02, 168.1;
31P NMR (162 MHz, CDCl3) δ11.0 and 12.5; LC/MS m/z 474
[M]þ. Anal. calcd for C25H31O7P: C 63.28; H 6.59. Found: C
63.45; H 6.51.
3
3H), 6.71 (d, J(H-H)=12.0 Hz, 1H, isomer 37d), 7.59-8.74
(m, 8H); 13C NMR (100 MHz, CDCl3) δ 13.3, 13.8, 14.00, 14.03,
14.1, 17.9, 20.4, 20.5, 21.95, 22.03, 22.1, 32.0, and 32.1 (2 d,
3J(P-C) = 5.0 and 7.0 Hz respectively), 35.5 (d, 3J(P-C) =
5.0 Hz, isomer 37c), 61.8, 61.9, 62.3, 63.3, 76.3, and 76.5 (2 d,
3J(P-C) = 7.0 and 5.0 Hz respectively), 76.90, 76.92, 125.4,
125.6, 126.0, 126.1, 126.5 (d, 3J(P-C) = 4.0 Hz), 127.0 (d,
3J(P-C) = 4.0 Hz), 127.3, 127.5, 127.7, 127.9, 128.1, 128.5,
128.6, 128.7, 128.8, 131.6 (d, 2J(P-C) = 18.0 Hz), 132.1 (d,
2J(P-C)=17.0 Hz), 133.5, 133.6, 133.7, 133.8, 133.9, 135.1 (d,
3J(P-C)=4.0 Hz), 138.4, 138.8 (d, 2J(P-C)=11.0 Hz), 142.3 (d,
2J(P-C)=9.0 Hz), 167.0, 167.5, 167.6; 31P NMR (162 MHz,
CDCl3) δ 9.9 and 11.3; LC/MS m/z 475 [M þ 1]þ. Anal. calcd for
C25H31O7P: C 63.28; H 6.59. Found: C 63.15; H 6.62.
Compounds 39(a-d). These compounds were prepared by a
procedure similar to that for 30a-c by using allenylphospho-
nate 11 (0.40 g, 1.20 mmol) and DMAD (0.62 g, 3.60 mmol).
Compound 39a: It was separated by using ethyl acetate/hexane
(1:1) mixture as the eluent. Yield quantitative [39aþ39bþ39(c,d),
ratio 3:2:5 by 31P NMR] 0.13 g (isolated, 22%, 39a); gummy;
IR (neat, cm-1) 2980, 2938, 1728, 1468, 1075, 1024, 835, 698; 1H
NMR (400 MHz, CDCl3) δ 0.76 and 0.82 (2 t, 3J(H-H)=7.6 Hz
each, 6H), 1.14 (m, 8H), 1.49 (qrt, 2H), 2.39 (s, 3H), 3.91 and
4.19 (m, 4H), 4.24 and 4.32 (2 qrt, 4H), 5.47 (d, 2J(P-H)=23.6
Hz, 1H), 7.22-8.00 (m, 7H); 13C NMR (100 MHz, CDCl3) δ 7.0,
7.1, 13.9, 14.1, 19.9, 22.5, 22.8, 37.3 (d, 3J(P-C)=5.0 Hz), 43.0
(d, 1J(P-C)=134.0 Hz), 61.4, 61.7, 73.4, and 73.5 (2 d, 3J(P-C)=
Compounds 38(a-d). These compounds were prepared by a
procedure similar to that for 30a-c using allenylphosphonate 11
(0.35 g, 1.1 mmol) and DMAD (0.45 g, 3.2 mmol). Compound
38a: It was separated by using ethyl acetate/hexane (2:3) mixture
as the eluent. Yield quantitative [38aþ38bþ38(c,d), ratio 3:2:5
by 31P NMR], 0.13 g (isolated, 24%, 38a); mp 132-134 °C; IR
(KBr, cm-1) 2963, 1742, 1721, 1601, 1433, 1281, 1196, 1076,
1032, 835, 787, 696, 517; 1H NMR (400 MHz, CDCl3) δ 0.77 and
0.82 (2 t, 3J(H-H)=6.0 and 8.0 Hz respectively, 6H), 1.19 and
1.49 (2 qrt, 4H), 2.38 (s, 3H), 3.80 and 3.85 (2 s, 6H), 3.87-4.16
(m, 4H), 5.45 (d, 2J(P-H)=24.0 Hz, 1H), 7.23-7.99 (m, 7H);
13C NMR (100 MHz, CDCl3) δ 7.0, 7.1, 19.9, 22.5, 22.8, 37.4 (d,
3J(P-C)=5.7 Hz), 43.1 (d, 1J(P-C)=133.4 Hz), 52.4, 52.6, 73.4,
2
8.0 and 7.0 Hz respectively), 127.4, 128.6, 129.6 (d, J(P-C)=
8.0 Hz), 132.1 (d, 3J(P-C)=5.0 Hz), 132.3, 132.8, 135.8, 168.0,
168.1; 31P NMR (162 MHz, CDCl3) δ 20.0; LC/MS m/z 502
[M]þ. Anal. calcd for C27H35O7P: C 64.53; H 7.02. Found: C
64.59; H 6.93. Compound 39b: It was separated by using ethyl
acetate/hexane (3:2) mixture as the eluent. Yield quantitative
[39aþ39bþ39(c,d)] by 31P NMR 0.11 g (isolated, 13%, 39b);
gummy; IR (neat, cm-1) 2975, 2938, 1732, 1603, 1470, 1416,
1287, 1192, 1076, 1032, 938, 843, 787, 700, 623; 1H NMR (400
3
MHz, CDCl3) δ 0.67 and 0.79 (2 t, J(H-H)=7.4 Hz and 7.6
respectively, 6H), 1.05-1.44 (m, 16H), 1.82 (d, 3J(H-H)=6.4
Hz, 3H), 3.92-4.32 (m, 12H), 5.79-5.87 (m, 2H), 6.43 (d,
2J(P-H)=16.0 Hz, 1H), 7.20-7.47 (m, 5H); 13C NMR (100
MHz, CDCl3) δ 7.00, 7.03, 13.5, 14.0, 18.8, 22.3, 23.4, 37.3 (d,
3J(P-C)=5.7 Hz), 45.0 (d,1J(P-C)=137.7 Hz), 61.8, 62.1, 73.1,
3
and 73.6 (2 d, J(P-C)=6.5 and 6.3 Hz respectively), 127.5,
3
128.7, 129.6, 129.7, 131.9, 132.3 (d, J(P-C)=5.1 Hz), 132.6,
133.1, 135.8 (d, J(P-C)=5.0 Hz), 136.1, 168.51, 168.54; 31P
3
3
NMR (162 MHz, CDCl3) δ 19.9; LC/MS m/z 475[M þ 1]þ.
Anal. calcd for C25H31O7P: C 63.28; H 6.59. Found: C 63.22;
H 6.65. Compound 38b: It was separated by using ethyl acetate/
hexane (2:3) mixture as the eluent. Yield quantitative
[38aþ38bþ38(c,d)] by 31P NMR, 0.10 g (isolated, 14%, 38b);
mp 124-126 °C; IR (KBr, cm-1) 2965, 1732, 1636, 1439, 1395,
1256, 1075, 941, 831, 733, 704; 1H NMR (400 MHz, CDCl3) δ
0.69 and 0.79 (2 t, 3J(H-H)=8.0 Hz each, 6H), 1.13 and 1.37
(2 qrt, 4H), 1.83 (d, 3J(H-H)=4.0 Hz, 3H), 3.62 and 3.79 (2 s,
12H), 3.93 (ddft, 2,3J ∼ 12.0 Hz, 2H), 4.18 (ddft, 2,3J ∼ 10.0 Hz,
2H), 5.74-5.86 (m, 2H), 6.42 (d, 2J(P-H) = 16.0 Hz, 1H),
7.21-7.47 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 7.0, 19.0,
22.3, 23.3, 37.4 (d, 3J(P-C)=5.0 Hz), 44.8 (d, 1J(P-C)=138.0
and 73.4 (2d, J(P-C)=6.4 and 6.8 Hz), 125.5, 126.9, 128.0,
130.4 (d, 2J(P-C)=9.9 Hz), 131.5 (d, 3J(P-C)=6.3 Hz), 133.5,
134.7, 135.0, 135.2, 135.6 (d, 3J(P-C)=7.7 Hz), 166.2, 167.1; 31
P
NMR (162 MHz, CDCl3) δ 17.8; LC/MS m/z 672 [M]þ. Anal.
calcd for C35H45O11P: C 62.49; H 6.74. Found: C 62.31; H 6.82.
Isomeric compounds 39(c,d): These compounds were separated
by using ethyl acetate/hexane (2:3) mixture as the eluent. Yield
quantitative [39aþ39bþ39(c,d)] by 31P NMR, 0.24 g (isolated,
40%, 39(c,d) ratio ∼1:1); gummy; IR (neat, cm-1) 2976, 2936,
1
1732, 1719, 1555, 1464, 1372, 1262, 1154, 1075, 1034, 938; H
NMR (400 MHz, CDCl3) δ 0.70-1.07 (m, 23H), 1.35-1.46 (m,
12H), 1.62 (d, J(H-H)=4.4 Hz, 3H, isomer 39c), 1.77-1.86
3
(m, 2H, isomer 39d), 3.57 and 3.60 (m each, 4H), 4.04-4.12 (m,
6H), 4.32 and 4.49 (2 qrt, 8H), 5.45-5.85 (m, 3H), 6.72 (d,
3J(H-H)=11.2 Hz, 1H, isomer 39d), 7.57-8.74 (m, 8H); 13C
NMR (100 MHz, CDCl3) δ 6.8, 7.3, 13.4, 13.9, 14.0, 14.10, 14.13,
18.0, 21.9, 22.1, 22.8, 35.5 (d, 3J(P-C)=3.6 Hz), 37.0 and 37.1 (2
d, 3J(P-C)=4.9 and 5.4 Hz respectively), 61.8, 61.9, 62.30, 62.34,
74.3, 74.4, 125.1, 125.5 (d, 3J(P-C)=4.0 Hz), 125.7 (d, 2J(P-C)=
3
Hz), 52.7, 52.9, 73.0, and 73.4 (2 d, J(P-C)=6.0 Hz each),
3
125.3, 127.1, 128.2, 130.1, 130.2, 131.8 (d, J(P-C)=7.0 Hz),
134.0, 134.8, 135.4 (d, 2J(P-C)=22.0 Hz), 135.6 (d, 3J(P-C)=
6.0 Hz), 166.7, 167.6; 31P NMR (162 MHz, CDCl3) δ 18.3; LC/MS
m/z 618 [M þ 1]þ. Anal. calcd for C31H37O11P: C 60.39; H
6.05. Found: C 60.29; H 6.12. Isomeric compounds 38(c,d): These
compounds were separated by using ethyl acetate/hexane (1:2)
mixture as the eluent. Yield quantitative [38aþ38bþ38(c,d)] by
31P NMR, 0.22 g (isolated, 42%, 38(c,d), ratio ≈ 1:1); gummy;
3
9.4 Hz), 125.9, 126.0, 126.1, 126.6, 126.7 (d, J(P-C)=4.1 Hz),
3
126.9, 127.1 (d, J(P-C) = 4.5 Hz), 127.5, 127.7, 127.9, 128.00,
128.04, 128.1, 128.3, 128.7, 128.8, 129.7, 129.8 (d, 3J(P-C)=5.3 Hz),
932 J. Org. Chem. Vol. 76, No. 3, 2011