[4R*,5R*,6S*]-1,7-Dioxaspiro[5.5]undecane-4,5-diol

Molecules 1997, 2, M19

[4R,5R,6S*]-1,7-Dioxaspiro[5.5]undecane-4,5-diol

Margaret A Brimble* and Andrew D Johnston

Division of Organic Chemistry, School of Chemistry F11, The University of Sydney, N.S.W 2006, Australia. phone +61-2-9351-2750, fax +61-2-9351-6650, e-mail [email protected], http://www.chem.usyd.edu.au/~brimble

Received: 18 June 1997 / Published: 20 June 1997

A solution of [3R*,4R*,5S*,6S*]-3,4-epoxy-1,7-dioxaspiro[5.5]undecan-5-ol (1) (561 mg, 3.01mmol) in dry tetrahydrofuran (30 ml) under a nitrogen atmosphere was cooled to 0 deg.C in an ice/water bath. Lithium aluminium hydride (4.52 ml, of a 1 mol L^-1solution in THF, 4.52 mmol) was added in 3 portions over 1 minute, and the reaction mixture allowed to stir at 0 deg.C for 1 h then room temperature for 12 h. After quenching with sodium dihydrogen phosphate solution (10 ml, 10% w/v), the reaction mixture was extracted with ethyl acetate (3x 50 ml), the combined extracts washed with water (10 ml) and dried over sodium sulphate. Removal of the solvent under reduced pressure gave a colourless oil, which was purified by flash chromatography using hexane-ethyl acetate (2:1) as eluent to afford [4R*,5R*,6S*]-1,7-Dioxaspiro[5.5]undecane-4,5-diol (2) (310 mg, 55%) as colourless needles [1].

M.p. 135-137 deg.C.

IR (Nujol) cm^-1 3600-3150 (br, s, OH), 1082 (s, C-O).

¹H-NMR (400 MHz, CDCl₃) 1.47 (1H, ddd, J_11ax,11eq 13.3, J_11ax,10ax 13.3 and J_11ax,10eq 4.4 Hz, 11ax-H), 1.54-1.81 (5H, m, 9-CH₂, 10-CH₂ and 3ax-H), 1.90 (1H, dt, J_11eq,11ax 13.3 and J_11eq,10 2.6 Hz, 11eq-H), 2.05-2.14 (1H, m, 3eq-H), 3.41 (1H, dd, J_5,4 7.4 and J_5,OH 3.7 Hz, 5-H), 3.62 (1H, ddd, J_2eq,
2ax 11.8, J_2eq,3ax 5.5 and J_2eq,3eq 2.3 Hz, 2eq-H), 3.71-3.99 (6H, m, 8-CH₂, 4-H, 2ax-H, 4-OH and 5-OH).

¹³C-NMR (100 MHz, CDCl₃) 17.6, 24.8, 27.6, 30.6 (CH₂, C-3, C-9, C-10 and C-11), 55.6 (CH₂, C-2), 61.3 (CH₂, C-8), 68.6 (CH, C-4), 71.1 (CH, C-5), 98.4 (quat, C-6).

CI-MS 189 (M⁺H, 85%), 171 (M⁺H-H₂O, 100), 153 (10), 118 (13), 115 (8), 101 (80), 83 (10).

Anal. calc. for C₉H₁₆O₄C, 57.44; H, 8.57%; M⁺H, 189.1127, found C, 57.50; H, 8.42%; M⁺H (CI, NH₃), 189.1134.

Acknowledgment: The authors gratefully acknowledge financial support from the Australian Research Council and The University of Sydney.

References and Notes

1. Another product (3 in the Scheme, a colourless glass, 33mg, 6%) will be reported in the following short note. Brimble, M. A.; Johnston, A. D. Molecules 1997, 2, M20.

Sample Availability: No sample available.