M. G. Kulkarni et al. / Tetrahedron: Asymmetry 21 (2010) 2394–2398
2397
(75 MHz, CDCl3): d 24.7, 46.4, 69.8, 70.5, 72.9, 109.4; Anal. Calcd for
C6H10O3: C, 55.37; H, 7.74. Found: C, 55.54; H, 7.65.
yield). ½a 2D8
ꢁ
¼ þ24:7 (c 1.05, CHCl3); IR (KBr): 2926, 1639, 1219,
1024 cmꢀ1 1H NMR (300 MHz, CDCl3): d 1.65–1.74 (m, 1H),
;
2.09–2.22 (m, 1H), 2.78–2.84 (m, 1H), 3.38 (br s, 1H, exchangeable
with D2O), 3.78–3.90 (m, 3H), 3.97 (dd, 1H, J = 10.2 and 3 Hz), 4.21
(d, 1H, J = 3 Hz), 5.87 (d, 1H, J = 4.7 Hz); 13C NMR: (75 MHz, CDCl3):
d 28.8, 51.9, 67.8, 75.2, 77.7, 108.8; Anal. Calcd for C6H10O3: C,
55.37; H, 7.74. Found: C, 55.58; H, 7.60.
4.4. (3R,3aS,6aR)-Hexahydrofuro[2,3-b]furan-3-yl benzoate 9
To a stirred solution of alcohol (ꢀ)-7 (1.02 g, 7.84 mmol), tri-
phenylphosphine (4.11 g, 15.7 mmol) and benzoic acid (1.91 g,
15.7 mmol) in dry THF (50 mL) at 23 °C was added diisoproylazo-
dicarboxylate (DIAD, 3.1 mL, 15.7 mmol). The resulting mixture
was stirred at that temperature for 1 h. After completion of the
reaction, the reaction was quenched by adding water. The layers
were separated and the aqueous layer was extracted with ethyl
acetate (25 mL ꢂ 3). The combined organic layer was dried over
anhydrous Na2SO4 and concentrated under reduced pressure. The
crude residue was purified by silica gel column chromatography
using ethyl acetate/pet ether (5:95) mobile phase to give benzoate
ester 9 as a colorless viscous liquid (1.68 g, 92% yield). IR (film):
Acknowledgment
Authors Y.B.S., A.S.B., A.P.D., S.W.C., D.R.B,. and R.G. thank the
CSIR, New Delhi for research fellowship.
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1721, 1458, 1274, 1023 cmꢀ1 1H NMR (300 MHz, CDCl3): d 1.89–
;
2.02 (m, 1H), 2.08–2.16 (m, 1H), 3.15–3.23 (m, 1H), 3.92–4.07
(m, 3H), 4.20 (dd, 1H, J = 9.9, 6.4 Hz), 5.44–5.51 (m, 1H), 5.81 (d,
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4.5. (3R,3aS,6aR)-Hexahydrofuro[2,3-b]furan-3-ol (ꢀ)-8
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yield). ½a 2D8
ꢁ
¼ ꢀ11:2 (c 1.2, MeOH); IR (film): 2924, 1633, 1263,
1008 cmꢀ1
;
1H NMR (300 MHz, CDCl3): d 1.81–1.94 (m, 1H),
2.28–2.36 (m, 1H), 2.51 (br s, 1H, exchangeable with D2O), 2.82–
2.91 (m, 1H), 3.63 (dd, 1H, J = 9.3 and 7.1 Hz), 3.86–4.02 (m, 3H),
4.45 (dd, 1H, J = 14.3 and 7.1 Hz), 5.69 (d, 1H, J = 5.5 Hz); 13C
NMR: (75 MHz, CDCl3): d 24.8, 46.5, 69.8, 70.7, 73.0, 109.5; Anal.
Calcd for C6H10O3: C, 55.37; H, 7.74. Found: C, 55.42; H, 7.68.
4.6. (3R,3aR,6aS)-Hexahydrofuro[2,3-b]furan-3-yl benzoate 10
Following a similar experimental procedure for the preparation
of benzoate ester 9, the bis-THF alcohol (+)-8 (938 mg, 7.21 mmol)
gave benzoate ester 10 as a colorless thick liquid (1.60 g, 95%
yield). IR (film): 1718, 1452, 1274, 1026 cmꢀ1
;
1H NMR
(300 MHz, CDCl3): d 1.91–2.00 (m, 1H), 2.21–2.34 (m, 1H), 2.99–
3.06 (m, 1H), 3.87–4.00 (m, 2H), 4.13 (d, 1H, J = 11.2 Hz), 4.18
(dd, 1H, J = 11.2, 2.9 Hz), 5.33 (d, 1H, J = 2.9 Hz), 5.95 (d, 1H,
J = 5.3 Hz), 7.45 (t, 2H, J = 7.6 Hz), 7.58 (t, 1H, J = 7.6 Hz), 8.04 (d,
2H, J = 7.6 Hz); 13C NMR: (75 MHz, CDCl3): d 29.1, 49.4, 67.9,
72.7, 80.3, 108.9, 128.4, 166.1; Anal. Calcd for C13H14O4: C, 56.65;
H, 6.02. Found: C, 56.79; H, 5.91.
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4.7. (3R,3aR,6aS)-Hexahydrofuro[2,3-b]furan-3-ol (+)-7
Following a similar experimental procedure for the hydrolysis
of benzoate ester 9, benzoate ester 10 (1.37 g, 5.85 mmol) gave
bis-THF alcohol (+)-7 as a white amorphous solid (705 mg, 93%