1098
S. Ghadigaonkar et al. / Tetrahedron: Asymmetry 23 (2012) 1093–1099
5.25 (m, 2H), 5.69–5.95 (m, 1H); 13C NMR: d ꢁ5.6, 18.1, 19.2, 19.6,
25.4, 25.8, 30.8, 38.0, 38.8, 59.0, 59.4, 61.6, 62.4, 72.9, 75.2, 94.4,
98.2, 114.4, 117.0, 138.3, 139.7. Anal. Calcd for C16H32O3Si: C,
69.95; H, 10.73. Found: C, 70.14; H, 10.79.
added to the residue, which was extracted with Et2O (3 ꢂ 10 mL).
The ether layer was washed with water (2 ꢂ 10 mL) and brine
(1 ꢂ 5 mL), dried, and concentrated in vacuo to give a residue,
which upon column chromatography (silica gel, 0–10% Et2O/hex-
ane) furnished pure 17. Yield: 0.267 g (84%); pale yellow liquid;
4.15. (3R)-3-Tetrahydropyranyloxy-pent-4-ene-1-ol 14
½
a 2D2
ꢃ
¼ þ92:7 (c 1.14, CHCl3), {lit.5f
½
a 2D5
ꢃ
¼ þ95:2 (c 0.85, CHCl3)};
IR: 1760 cmꢁ1 1H NMR: d 2.42–2.48 (m, 2H), 4.84–4.92 (m, 1H),
;
To a cooled (0 °C) and stirred solution of 13 (1.0 g, 3.33 mmol) in
THF (15 mL) was added Bu4NF (5.0 mL, 1 M in THF, 5.0 mmol). The
reaction mixture was brought to room temperature and stirred un-
til the reaction was complete (cf. TLC, 3 h). The mixture was poured
into ice-cold water (15 mL) and extracted with EtOAc (2 ꢂ 10 mL).
The organic extract was washed with water (2 ꢂ 10 mL) and brine
(1 ꢂ 5 mL), and dried. Removal of the solvent followed by column
chromatography of the residue (silica gel, 0–15% EtOAc/hexane)
5.25–5.44 (m, 2H), 5.85–6.02 (m, 1H), 6.16 (d, J = 11.5 Hz, 1H),
6.72–6.78 (m, 1H); 13C NMR: d 29.3, 71.9, 114.8, 121.6, 134.8,
145.1, 166.8.
4.19. (6R)-6-[(E,4’S,6’S)-4,6-Dihydroxy-8-phenyl-1-octenyl]-5,6-
dihydropyran-2-one 1
A solution of (4S,6S)-7c (0.110 g, 0.5 mmol) and 17 (0.155 g,
12.5 mmol) in dry CH2Cl2 (20 mL) was degassed with bubbling ar-
gon. Next, Grubbs’ 2nd generation catalyst (5 mol %) was added
and the mixture heated under argon at 50 °C for 3 h. After cooling,
the mixture was concentrated in vacuo, and the residue was puri-
fied by column chromatography (silica gel, 0–15% EtOAc/hexane)
to give pure 1. Yield: 0.087 g (55%); white solid; mp: 115 °C, (lit.5f
furnished 14. Yield: 0.564 g (91%); colorless liquid; ½a D22
¼ þ24:8
ꢃ
(c 1.43, CHCl3); IR: 3478 cmꢁ1 1H NMR: d 1.51–1.70 (m, 5H),
;
1.73–1.84 (m, 3H), 2.57 (broad s, 1H), 3.47–3.52 (m, 1H), 3.69–
3.88 (m, 3H), 4.24–4.34 (m, 1H), 4.72 and 4.78 (two m, 1H), 5.12–
5.27 (m, 2H), 5.66–5.93 (m, 1H); 13C NMR: d 19.2, 19.6, 25.5, 25.8,
30.4, 30.6, 38.3, 60.4, 60.8, 61.8, 62.3, 71.9, 72.7, 94.6, 97.9, 114.4,
116.8, 138.0, 139.5. Anal. Calcd for C10H18O3: C, 64.49; H, 9.74.
Found: C, 64.70; H, 9.89.
mp: 109–114 °C); ½a D22
ꢃ
¼ þ35:4 (c 1.14, CHCl3), {lit.5f
½
a 2D7
¼ þ54:1 (c
ꢃ
þ 37:8 (c
0.5, CHCl3), lit.3
½
a 2D4
ꢃ
¼ þ81:6 (c 0.52, CHCl3), lit.5e
½
a 2D4
ꢃ
0.33, CHCl3)}; IR: 1742 cmꢁ1; 1H NMR: d 1.59–1.81 (m containing a
tat d 1.71, J = 6.2 Hz, 4H), 2.26–2.32 (m, 2H), 2.40–2.44 (m, 2H),
2.55–2.80 (m, 2H), 3.84–4.02 (m, 2H), 4.84–4.91 (m, 1H), 5.54–
5.61 (m, 1H), 5.81–5.88 (m, 1H), 6.00 (dt, J = 9.3, 2.1 Hz, 1H),
6.84–6.92 (m, 1H), 7.17–7.32 (m, 5H); 13C NMR: d 29.8, 38.0,
38.7, 40.4, 42.3, 68.3, 68.8, 77.9, 121.6, 126.0, 128.5, 129.9, 131.0,
131.4, 142.0, 145.0, 164.2.
4.16. (3R)-3-Tetrahydropyranyloxypent-4-enal 15
As described above, oxidation of alcohol 14 (1.0 g, 5.38 mol) PCC
(1.73 g, 8.06 mmol) and NaOAc (0.1 equiv) in CH2Cl2 (40 mL) fol-
lowed by work-up furnished pure 15. Yield: 0.870 g (88%); colorless
liquid; ½a 2D2
ꢃ
¼ þ29:1 (c 1.22, CHCl3); IR: 2717, 1718 cmꢁ1; 1H NMR:
d 1.57–1.78 (m, 6H), 2.29–2.38 (m, 2H), 3.75–3.87 (m, 2H), 4.34–
4.42 (m, 1H), 4.68 and 4.76 (two m, 1H), 5.16–5.28 (m, 2H), 5.71–
5.91 (m, 1H), 9.68 (t, J = 2.1 Hz, 1H); 13C NMR: d 18.9, 19.7, 25.6,
25.8, 30.4, 31.2, 37.7, 62.1, 62.3, 72.1, 72.5, 95.1, 98.0, 116.1,
116.5, 139.1, 139.7, 202.8. Anal. Calcd for C10H16O3: C, 65.19; H,
8.75. Found: C, 64.70; H, 9.89.
References
1. Hoffmann, H. M. R.; Rabe, J. Angew. Chem., Int. Ed. Engl. 1985, 24, 94–110.
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Rojas, C. M. Tetrahedron 2001, 57, 47–53; (c) Murga, J.; Falomoir, E.; Garcia-
Fortanet, J.; Carda, M.; Marco, J. A. Org. Lett. 2002, 4, 3447–3449.
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Phytochemistry 2000, 54, 989–993.
4.17. Ethyl (5R,2Z)-5-tetrahydropyranyloxyhepta-2,6-dienoate
16
4. (a) Juliawaty, L. D.; Watanabe, Y.; Kitajima, M.; Achmad, S. A.; Takayama, H.;
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Enders, D.; Lenzen, A.; Muller, M. Synthesis 2004, 1486–1496; (f) Sabitha, G.;
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184–191; (g) Tang, S.; Xie, X.; Wang, X.; He, L.; Xu, K.; She, X. J. Org. Chem. 2010,
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6. (a) Nicolaou, K. C.; Vourloumis, D.; Winssinger, N.; Baran, P. S. Angew. Chem.,
Int. Ed. 2000, 39, 44–122; (b) Corey, E. J.; Guzman-Perez, A. Angew. Chem., Int.
Ed. 1998, 37, 388–401; (c) Noyori, R. Asymmetric Catalysis in Organic Synthesis;
Wiley: New York, 1994.
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1998, 16, 210–215.
To a cooled (0 °C) and stirred suspension of pentane-washed
NaH (0.140 g, 2.91 mmol, 50% suspension in oil) in THF (5 mL)
was added ethyl (diphenylphosphono)acetate (0.930 g, 2.91 mmol)
in THF (5 mL). After 15 min, when the solution became clear, alde-
hyde 15 (0.450 g, 2.45 mmol) in THF (5 mL) was injected into it.
After stirring at room temperature for 18 h, the mixture was
poured into ice-water and extracted with Et2O (3 ꢂ 10 mL). The
ether layer was washed with water (2 ꢂ 10 mL) and brine
(1 ꢂ 5 mL), dried, and concentrated in vacuo to give a residue,
which upon column chromatography (silica gel, 0–10% Et2O/hex-
ane) furnished pure Z-16. Yield: 0.480 g (77%); colorless liquid;
½
a 2D2-40.1 (c 1.12, CHCl3); IR: 1742 cmꢁ1 1H NMR: d 1.29 (t,
;
ꢃ
9. (a) Sharma, A.; Chattopadhyay, S. J. Org. Chem. 1998, 63, 6128–6131; (b)
Sharma, A.; Chattopadhyay, S. J. Org. Chem. 1999, 64, 8059–8062; (c) Sharma,
A.; Gamre, S.; Chattopadhyay, S. Lett. Org. Chem. 2005, 2, 547–549; (d) Kumar,
A. N.; Bhatt, S.; Chattopadhyay, S. Tetrahedron: Asymmetry 2009, 20, 205–209.
10. (a) Maity, B.; Chattopadhyay, S. Curr. Bioact. Compd. 2008, 4, 225–244; (b)
Guha, P.; Dey, A.; Sarkar, B.; Dhyani, M. V.; Chattopadhyay, S.; Bandyopadhyay,
S. K. J. Exp. Pharmacol. Ther. 2009, 328, 1–10; (c) Guha, P.; Dey, A.; Chatterjee, A.;
Chattopadhyay, S.; Bandyopadhyay, S. K. Br. J. Pharmacol. 2010, 159, 726–734;
(d) Patro, B. S.; Maity, B.; Chattopadhyay, S. Antioxid. Redox Signal. 2010, 12,
945–960; (e) Patro, B. S.; Tyagi, M.; Saha, J.; Chattopadhyay, S. Bioorg. Med.
Chem. 2010, 18, 7043–7051; (f) Yadav, S. K.; Adhikary, B.; Chand, S.; Maity, B.;
Bandyopadhyay, S. K.; Chattopadhyay, S. Free Radical Biol. Med. 2012, 52, 1175–
1187; (g) Maity, B.; Yadav, S. K.; Patro, B. S.; Bandyopadhyay, S. K.;
Chattopadhyay, S. Free Radical Biol. Med. 2012, 52, 1680–1691.
J = 7.4 Hz, 3H), 1.54–1.60 (m, 4H), 1.69–1.75 (m, 1H), 1.83–1.85
(m, 1H), 2.94–3.03 (m, 2H), 3.50–3.52 (m, 1H), 3.86–3.90 (m,
1H), 4.18 (q, J = 7.4 Hz, 2H), 4.24–4.30 (m, 1H), 4.67–4.70 and
4.75–4.77 (two m, 1H), 5.15–5.32 (m, 2H), 5.67–5.73 (m, 1H),
5.88 (d, J = 11.5 Hz, 1H), 6.26–6.42 (m, 1H); 13C NMR: d 14.2,
19.4, 25.4, 25.5, 30.6, 30.7, 33.3, 34.9, 59.7, 62.3, 75.5, 75.9, 95.2,
97.0, 115.3, 117.5, 120.9, 121.3, 137.6, 138.6, 145.2, 145.8, 166.2.
Anal. Calcd for C14H22O4: C, 66.12; H, 8.72. Found: C, 64.70; H, 9.89.
4.18. (5R,2Z)-Hepta-2,6-dien-5-olide 17
11. For reviews on olefin metathesis, see: (a) Armstrong, S. K. J. Chem. Soc., Perkin
Trans. 1 1998, 371–388; (b) Schrock, R. R. Tetrahedron 1999, 55, 8141–8153; (c)
Fürstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012–3043; (d) Trnka, T. M.;
Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18–29; (e) Blackwell, H. E.; O’Leary, D. J.;
A solution of 16 (0.650 g, 2.56 mmol) and PPTS (cat.) in MeOH
(20 mL) was stirred at room temperature for 12 h. The mixture
was then concentrated in vacuo, after which water (15 mL) was