2
806
J. S. Yadav, S. S. Mandal
LETTER
Spectroscopic Data for Representative Compounds 2
Biomol. Chem. 2004, 2, 2050. (h)Austin, K. A. B.; Banwell,
M. G.; Loong, D. T. J.; Rae, A. D.; Willis, A. C. Org.
Biomol. Chem. 2005, 3, 1081. (i) Rajesh, K.; Suresh, V.;
Selvam, J. J. P.; Rao, C. B.; Venkateswarlu, Y. Synthesis
1
b
Colorless solid; mp 100–101 °C (lit. mp 98–102 °C);
2
9
1b
[a]D +24.2 (c 1.5, CHCl ) {lit. [a] +26.9 (c 0.4,
3
D
1
MeOH)}. H NMR (300 MHz, CDCl ): d = 1.27 (d, 3 H,
J = 6.0 Hz, H-12), 1.34–2.08 (m, 10 H, 5 × CH ), 2.45 (br s,
3
2
010, 1381. (j) Kaliappan, K.; Si, D. Synlett 2010, 2441.
2
(
(
6) For the synthesis of cladospolide D, see: (a) Lu, K.-J.;
2-OH), 3.88 (dtd, 1 H, J = 1.5, 4.0, 8.6 Hz, H-5), 4.97 (qdd,
1 H, J = 0.3, 6.0, 9.2 Hz, H-11), 5.11 (ddd, 1 H, J = 1.2, 4.0,
8.6 Hz, H-4), 5.85 (dd, 1 H, J = 1.1, 12.0 Hz, H-2), 6.13 (dd,
Chen, C.-H.; Hou, D.-R. Tetrahedron 2009, 65, 225.
b) Xing, Y.; O’Doherty, G. A. Org. Lett. 2009, 11, 1107.
c) Xing, Y.; Penn, J. H.; O’Doherty, G. A. Synthesis 2009,
(
(
2
1
3
1 H, J = 8.6, 12.0 Hz, H-3). C NMR (75 MHz, CDCl ): d =
3
847.
17.3, 20.3, 20.5, 25.0, 29.6, 30.9, 67.9, 72.5, 73.1, 122.3,
145.2, 166.1. IR (neat): 3454, 3298, 2927, 2859, 1710, 1463,
7) For the synthesis of the revised structure of isocladospolide
B, see: (a) Sharma, G. V. M.; Reddy, J. J.; Reddy, K. L.
Tetrahedron Lett. 2006, 47, 6537. (b) Ferrié, L.; Reymond,
S.; Capdevielle, P.; Cossy, J. Synlett 2007, 2891. For other
syntheses of the structure of isocladospolide B, see:
–
1
+
1285, 1106, 1043, 823 cm . ESI-MS: m/z = 251 [M + Na] .
+
ESI-HRMS: m/z calcd for C H O Na [M + Na] : 251.1259;
1
2
20
4
found: 251.1267.
Compound 3
1
b
31
(
c) Franck, X.; Vaz Araujo, M. E.; Jullian, J.-C.;
Hocquemiller, R.; Figadere, B. Tetrahedron Lett. 2001, 42,
801. (d) Pandey, S. K.; Kumar, P. Tetrahedron Lett. 2005,
6, 6625. (e) Trost, B. M.; Aponick, A. J. Am. Chem. Soc.
006, 128, 3931. (f) Srihari, P.; Bhasker, E. V.;
Colorless solid; mp 92–93 °C (lit. mp 90–91 °C); [a]D
1a
+36.7 (c 0.3, CHCl ) {lit. [a] +59.7 (c 0.4, MeOH)}.
3
D
1
2
4
2
H NMR (300 MHz, CDCl ): d = 1.31 (d, 3 H, J = 6.0 Hz, H-
3
12), 1.23–1.28 (m, 10 H, 5 × CH ), 2.54 (br s, OH), 3.56 (t,
1 H, J = 7.7 Hz, H-5), 3.98 (dd, 1 H, J = 7.7, 9.1 Hz, H-4),
4.92–5.02 (m, 1 H, H-11), 6.05 (d, 1 H, J = 15.8 Hz, H-2),
2
Harshavasdhan, S. J.; Yadav, J. S. Synthesis 2006, 4041.
1
3
(8) For our contributions on lactone-containing molecules, see:
6.81 (dd, 1 H, J = 9.4, 15.8 Hz, H-3). C NMR (75 MHz,
(
a) Yadav, J. S.; Mandal, S. S.; Reddy, J. S. S.; Srihari, P.
CDCl ): d = 20.8, 24.5, 27.2, 29.7, 32.1, 33.9, 74.4, 76.6,
3
Tetrahedron 2011, 67, 4620. (b) Yadav, J. S.; Reddy, J. S.
S.; Mandal, S. S.; Srihari, P. Synlett 2010, 2636. (c) Srihari,
P.; Kumaraswamy, B.; Rao, G. M.; Yadav, J. S.
77.5, 124.5, 145.3, 166.1. IR (neat): 3321, 1725, 1637, 1352,
–
1
+
1219, 1109, 772 cm . ESI-MS: m/z = 251 [M + Na] . ESI-
+
HRMS: m/z calcd for C H O Na [M + Na] : 251.1259;
1
2
20
4
Tetrahedron: Asymmetry 2010, 21, 106. (d) Srihari, P.;
Bhasker, E. V.; Reddy, A. B.; Yadav, J. S. Tetrahedron Lett.
found: 251.1269.
Compound 5
2
9
2b
2
009, 50, 2420. (e) Yadav, J. S.; Kumar, V. N.; Rao, R. S.;
Colorless syrup; [a] –56.6 (c 1.0, CHCl ) {lit. [a] –61.0
D
3
D
1
Srihari, P. Synthesis 2008, 1938. (f) Srihari, P.; Kumar, B.
(c 16.6, MeOH)}. H NMR (300 MHz, CDCl ): d = 1.17 (d,
3
P.; Subbarayudu, K.; Yadav, J. S. Tetrahedron Lett. 2007,
3 H, J = 6.0 Hz, H-12), 1.20–1.63 (m, 10 H, 5 × CH ), 1.82
2
48, 6977. (g) Srihari, P.; Bhasker, E. V.; Harshavardhan, S.
(br s, 2-OH), 3.70–3.84 (m, 2 H, H-11, H-5), 4.98 (ddd, 1 H,
J.; Yadav, J. S. Synthesis 2006, 4041. (h) Yadav, J. S.; Rao,
K. V.; Sridhar Reddy, M.; Prasad, A. R. Tetrahedron Lett.
J = 1.5, 2.3, 4.5 Hz, H-4), 6.18 (dd, 1 H, J = 2.3, 6.0 Hz, H-
2), 7.46 (dd, 1 H, J = 1.5, 6.0 Hz, H-3). C NMR (75 MHz,
1
3
2
006, 47, 4393. (i) Yadav, J. S.; Prathap, I.; Padmaja, T. B.
CDCl ): d = 23.9, 25.8, 25.9, 29.7, 33.5, 39.5, 68.5, 72.1,
3
Tetrahedron Lett. 2006, 47, 3773.
86.6, 123.1, 154.2, 173.4. IR (neat): 3452, 3370, 2930, 2854,
–
1
+
(
9) (a) Schaus, S. E.; Brandes, B. D.; Larrow, J. F.; Tokunaga,
M.; Hansen, K. B.; Gould, A. E.; Furrow, M. E.; Jacobsen,
E. N. J. Am. Chem. Soc. 2002, 124, 1307. (b) For earlier
publications from our group using salen complexes, see:
Yadav, J. S.; Srihari, P. Tetrahedron: Asymmetry 2004, 15,
1748, 1465, 1172, 831 cm . ESI-MS: m/z = 251 [M + Na] .
+
ESI-HRMS: m/z calcd for C H O Na [M + Na] : 251.1259;
1
2
20
4
found: 251.1271.
Compound 12
[a]D +18.7 (c 1.0, CHCl ). H NMR (300 MHz, CDCl ):
3
0
1
3
3
81.
d = 0.02 (s, 6 H), 0.87 (s, 9 H), 1.09 (d, 3 H, J = 6.0 Hz),
1.23–1.59 (m, 8 H), 1.74–2.16 (m, 2 H), 2.27–2.55 (m, 1 H),
3.36 (d, 3 H, J = 3.6 Hz), 3.63 (br s, OH), 3.68–3.81 (m, 1
H), 3.83–4.07 (m, 1 H), 4.54 (dd, 1 H, J = 4.2, 6.6 Hz), 4.68
(d, 3 H, J = 6.6 Hz), 5.23–5.37 (m, 2 H), 5.57–5.86 (m, 1 H).
(
(
10) (a) Brown, H. C.; Jadhav, P. K.; Bhat, K. S. J. Am. Chem.
Soc. 1988, 110, 1535. (b) The de was determined to be
>
99% by reverse-phase HPLC column chromatography:
Waters HRC18, 300 × 3.9 mm, 6 micron. The mobile phase
used was MeCN + H O (30:70). Flow rate: 1.0 mL/min. The
ee was analyzed using Chiral Pack IA, 250 × 4.6 mm, 5 mm,
l = 254 nm, hexane–2-PrOH (80:20) as mobile phase, flow
rate: 1.0 mL/min.
1
3
C NMR (75 MHz, CDCl ): d = –4.7, –4.5, 18.1, 23.8, 25.7,
2
3
25.9, 29.7, 32.1, 34.3, 39.6, 55.5, 68.6, 73.2, 80.8, 93.8,
120.0, 133.6. IR (neat): 3436, 2927, 2857, 1641, 1460, 1031,
769 cm . ESI-MS: m/z = 383 [M + Na] . ESI-HRMS:
–
1
+
+
11) (a) Still–Gennari olefination of the aldehyde 14 derived from
m/z calcd for C H O NaSi [M + Na] : 383.2593; found:
1
9
40
4
7
leading to 6 was performed according to the literature
procedure: Still, W. C.; Gennari, C. Tetrahedron Lett. 1983,
4, 4405. (b) For a review on Wittig olefination reactions,
see: Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89,
63.
383.2579.
Compound 15
3
1
1
2
[a]D +23.6 (c 1.0, CHCl ). H NMR (300 MHz, CDCl ):
3
3
d = 1.19 (d, 3 H, J = 6.0 Hz), 1.42 (s, 3 H), 1.43 (s, 3 H),
1.28–1.72 (m, 10 H), 3.69–3.78 (m, 1 H), 3.83 (q, 1 H,
J = 6.0 Hz,), 5.27 (dt, 1 H, J = 1.0, 9.0 Hz), 5.64 (br s, 2-
OH), 5.94 (dd, 1 H, J = 1.0, 11.3 Hz), 6.23 (dd, 1 H, J = 8.3,
8
(
(
12) Keck, G. E.; Murry, J. A. J. Org. Chem. 1991, 56, 6606.
13) Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi,
M. Bull. Chem. Soc. Jpn. 1979, 52, 1989.
1
3
11.3 Hz). C NMR (75 MHz, CDCl ): d = 23.1, 25.0, 25.1,
3
(
(
14) Shiina, I.; Kubota, M.; Ibuka, R. Tetrahedron Lett. 2002, 43,
27.0, 27.3, 29.3, 31.6, 38.7, 68.2, 76.0, 80.8, 109.3, 122.4,
147.4, 169.1. IR (neat): 3473, 2934, 1722, 1661, 1371, 1174,
7535.
15) The H NMR and 13C NMR spectroscopic data, specific
1
1036, 979 cm . ESI-MS: 309 [M + Na] . ESI-HRMS: m/z
calcd for C H O NaSi [M + Na] : 309.1682; found:
–1
+
+
rotation, and mp match the reported data for cladospolide B
1
5
26
4
(
2), cladospolide C (3), and isocladospolide B (5).
309.1678.
Synlett 2011, No. 19, 2803–2806 © Thieme Stuttgart · New York