(400 MHz, CDCl3): δ 6.82-6.88 (dd, J = 5.7, 15.8 Hz, 1H),
80.86, 66.77, 62.07, 38.45, 27.17, 2A6.9C5,C2E3.7P0T, E23D.52M.; ANUSCRIPT
GC-MS (ES): 229 [M+-15].
6.08-6.12 (dd, J = 1.4 Hz, 15.6 Hz, 1H), 4.11-4.23 (m,
3H), 3.69–3.80 (m, 2H), 1.40–1.64 (m, 19H), 1.16-1.18 (d,
J = 6.2 Hz, 3H).; 13C NMR (100 MHz, CDCl3): δ 166.05,
144.11, 122.74, 109.336, 80.58, 80.56, 68.04, 60.62, 39.16,
31.95, 29.55, 27.26, 25.94, 25.54, 23.49, 14.21.; GC-MS
(ES): 299 [M+-15].
20
Compound 22b: Viscous oil.; [α]D = +3.0(c 0.2,
CHCl3).; IR (CHCl3, cm-1): 3429, 3015, 2989, 2932, 1634,
1373, 1216, 1057, 843, 755, 667 cm-1; 1H NMR (400 MHz,
CDCl3): δ1.17-1.19 (d, J = 6.2 Hz, 3H), 1.40 (s, 3H), 1.42
(s, 3H), 1.47-1.53 (m 2H), 2.06-2.51 (m, 5H), 3.58-3.65
(m, 2H), 3.73-3.80 (m, 3H), 3.89-3.96 (m, 1H), 5.43-5.56
(m, 2H).; 13C NMR (100 MHz, CDCl3): δ 132.31, 124.67,
108.72, 80.85, 66.75, 62.02, 38.44, 27.19, 26.96, 23.77,
23.53.; GC-MS (ES): 229 [M+-15].
Acknowledgments
The authors would like to thank Dr. H. Rama Mohan and
Dr. Reddy’s Laboratories for their support and
encouragement. We also thank analytical department of Dr.
Reddy’s Laboratories Ltd for providing analytical support.
4.3.1.10.
Synthesis
of
(R)-7-((4S,
5S)-5-
(hydroxymethyl)-2,
2-dimethyl-1,
3-dioxolan-4-yl)
heptan-2-ol (8a): To a solution of 22a(1.8 g, 7.3 mmole)
in ethyl acetate (36 mL) at rt added 20% Pd(OH)2 by
wt.and hydrogenated for 4 h at 40psi, upon completion of
reaction catalyst was removed by filtration, thus obtained
filtrate was evaporated to afford 8a (1.75 g, 96 %).
Similarly antipode 8b was synthesized from 22busing
above procedure to afford (1.88g, 98%). Compound 8a:
References and notes
1. (a) Hirota, A.; Isogai, A.; Sakai, H. Agric. Biol. Chem.
1981, 45, 799; (b) Hirota, A.; Sakai, H.; Isogai, A.;
Kitano, Y.; Ashida, T.; Hirota, H.; Takahashi, T. Agric.
Biol. Chem. 1985, 49, 903; (c) Hirota, H.; Hirota, A.;
Sakai, H.; Isogai, A.; Takahashi, T. Bull. Chem. Soc.
Jpn. 1985, 58, 2147; (d) Hirota, A.; Sakai, H.; Isogai,
A. Agric. Biol. Chem. 1985, 49, 731.
20
Colorless oil.; [α]D = + 2.33 (c 0.2, CHCl3).; IR (CHCl3,
cm-1): 3450, 2988, 2965, 2933, 2860, 1438, 1457, 1379,
1
1243, 1050, 756, 666.; H NMR (400 MHz, CDCl3): δ
1.16-1.18 (d, J = 6.2 Hz, 3H), 1.33-2.12 (m, 18H), 3.56-
3.60 (m, 1H), 3.69-3.89 (m 4H).; 13C NMR (100 MHz,
CDCl3): δ 23.49, 25.55, 25.57, 25.95, 27.01, 27.37, 29.59,
32.93, 39.16, 61.97, 68.05, 81.43, 108.57.; HRMS (ESI+):
Calcd. for C13H27O4+H: 247.1909 found: 247.1899.
2. Fujii, Y.; Fukuda, A.; Hamasaki, T.; Ichimoto, I.;
Nakajima, H. Phytochemistry1995, 40, 1443.
3. Smith, C. J.; Abbanat, D.; Bernan, V. S.; Maiese, W.
M.; Greenstein, M.; Jampa, J.; Tahir, A.; Ireland, C. M.
J. Nat. Prod. 2000, 63, 142.
4. (a) Zhang, H.; Tomoda, H.; Tabata, N.; Miura, H.;
Namikoshi, M.; Yamaguchi, Y.; Masuma, R.; Omura,
S. J. Antibiot. 2001, 54, 635. (b) Chada, R, R.; Devatha,
S.; Nagavaram, N, R.; Eur. J. Org. Chem. 2013, 18,
3786-3796
20
Compound 8b: Colorless oil.; [α]D = -3.11 (c 0.2,
CHCl3).; IR (CHCl3, cm-1): 3435, 3018, 2990, 2934, 2860,
1458, 1372, 1215, 770, 669.; 1H NMR (400 MHz, CDCl3):
δ 1.16-1.17 (d, J = 6.2 Hz, 3H), 1.33-1.79 (m, 18H), 3.56-
3.60 (m, 1H), 3.69-3.80 (m 3H), 3.84-3.87 (m, 1H).; 13C
NMR (100 MHz, CDCl3): δ 23.47, 25.55, 25.94, 27.01,
27.36, 29.56, 32.91, 61.99, 68.05, 81.46, 108.58.; GC-MS
(ES): 231 [M+-15].
5. (a) Si, D.; Sekar, N. M.; Kaliappan, K. P.; Org. Biomol.
Chem. 2011, 9, 6988; (b) Rajesh, K.; Suresh, V.;
Selvam, J. J. P.; Rao, C. B.; Venkateswarlu, Y.
Synthesis, 2010, 1381; (c) Kaliappan, K. P.; Si, D.
Synlett, 2009, 2441; (d) Banwell, M. G.; Loong, D. T.
J. Org. Biomol. Chem. 2004, 2, 2050; (e) Banwell, M.
G.; Jolliffe, K. A.; Loong, D. T. J.; McRae, K. J.;
Vounatsos, F.J. Chem. Soc. Perkin Trans. 1 2002, 22;
(f) Solladié, G.; Almario, A.; Tetrahedron: Asymmetry
1995, 6, 559; g) Solladié, G.; Antonio, A.; Pure Appl.
Chem. 1994, 66, 2159; (h) Ichimoto, I.; Sato, M.;
Kirihata, M.; Ueda, H.; Chem. Express, 1987, 2, 495;
(i) Maemoto, S.; Mori, K. Chem. Lett. 1987, 109; (j)
Mori, K.; Maemoto, S. Liebigs Ann. Chem. 1987, 863.
6. (a) Yadav, J. S.; Mandal, S. S. Synlett, 2011, 19, 2803;
(b) Prasad, K. R.; Gandi, V. R. Tetrahedron:
Asymmetry, 2011, 22, 499; (c) Xing, Y.; O’Doherty, G.
A. Org. Lett. 2009, 11, 1107; d) Wang, W.-K.; Zhang,
J.-Y.; He, J.-M.; Tang, S.-B.; Wang, X.-L.; She, X.-G.;
Pan, X.-F. Chin. J. Chem. 2008, 26, 1109; (e) Sharma,
G. V. M.; Reddy, J. J. R.; Reddy, K. L. Tetrahedron
Lett. 2006, 47, 6537; (f) Sharma, G. V. M.; Reddy, J. J.
R.; Reddy, K. L. Tetrahedron Lett. 2006, 47, 6531; (g)
Pandey, S. K.; Kumar, P. Tetrahedron Lett. 2005, 46,
6625; (h) Austin, K. A. B.; Banwell, M. G.; Loong, D.
T. J.; Rae, D.; Willis, A. C. Org. Biomol. Chem. 2005,
3, 1081.
2.1.11. Synthesis of Ethyl (E)-3-{(4S, 5S)-5-[(R)-6-
Hydroxyheptyl]-2,
2-dimethyl-1,
3-dioxolan-4-
yl}acrylate (9a): To diol 8a (175 mg, 0.71 mmol) in
CH2Cl2 (3 mL) at 0 °C were added BAIB (263 mg, 0.81
mmol) and TEMPO (10 mg, 0.06 mmol). After stirring at
room temperature for 2 h, the mixture was cooled to 0 °C,
and (ethoxycarbonylmethylene) triphenylphosphorane (21)
(320 mg, 0.92 mmol) was added. The stirring was
continued for another 2 h at room temperature. After
completion of the reaction, the mixture was concentrated
under reduced pressure. The residue was purified by
column chromatography (hexanes/EtOAc) to afford α, β-
unsaturated ester 9a (210 mg, 94%). Similarly
diastereomer 9b synthesized from 8b using above
procedure to afford (195 mg, 88%). Compound 9a: Pale
20
yellow liquid.; [α]D = +10 (c 0.1, CHCl3).; IR (CHCl3,
cm–1): 3504, 2984, 2933, 2860, 2250, 1716, 1660, 1459,
1
1373, 1240, 1168, 1103, 1036, 907, 725, 647.; H NMR
(400 MHz, CDCl3): δ 6.82-6.87 (dd, J = 5.8, 15.6 Hz, 1H),
6.08-6.12 (d, J = 15.6 Hz, 1H), 4.16-4.23 (m, 2H), 4.11–
4.15 (m, 1H), 3.67–3.82 (m, 2H), 1.27–1.62 (m, 19H),
1.16-1.18 (d, J = 6.16Hz, 3H).; 13C NMR (100 MHz,
CDCl3): δ 166.02, 144.11, 122.73, 109.34, 80.21, 68.03,
60.59, 39.15, 31.96, 29.54, 27.24, 26.63, 25.91, 25.54,
23.49, 14.18.; GC-MS (ES): 299 [M+-15].
7. (a) Reddy, C. R.; Rao, N. N.; Sujitha, P.; Kumar, C. G.
Synthesis, 2012, 44, 1663; (b) Trost, B. M.; Aponick,
A. J. Am. Chem. Soc. 2006, 128, 3931; (c) Srihari, P.;
Bhasker, E. V.; Harshavardhan, S. J.; Yadav, J. S.
Synthesis, 2006, 4041; d) Franck, X.; Araujo, M. E. V.;
20
Compound 9b: Pale yellow liquid., [α]D = -7.9 (c 0.1,
CHCl3).; IR (CHCl3, cm–1): 3528, 3018, 2988, 2936, 2881,
1
1717, 1662, 1459, 1371, 1216, 1035, 756, 668.; H NMR