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Short Note

[2R*,5S*,6S*]-2-Methyl-1,7-dioxaspiro[5.5]undec-3-en-5-ol§

by
Margaret A. Brimble
* and
Andrew D. Johnston
Division of Organic Chemistry, School of Chemistry F11, The University of Sydney, N.S.W 2006, Australia
*
Author to whom correspondence should be addressed.
Molecules 1997, 2(6), M15; https://doi.org/10.3390/M15
Submission received: 16 June 1997 / Published: 20 June 1997
(This article belongs to the Section Molbank Section of Molecules, 1997-2001)
Versions Notes
Molecules 02 m15 i001
Isomerisations of epoxides to allylic alcohols have been effected by strong non-nucleophilic bases such as lithium dialkylamides. The formation of allylic alcohols from the reaction of epoxides with lithium amide bases appears to proceed via a b-elimination pathway when the reaction is performed in relatively non-polar solvents [1].
To a solution of dry diethylamine (0.085 ml, 0.82 mmol) in dry hexane (40 ml) under a nitrogen atmosphere at -35 deg.C, was added n-butyllithium (1.3 ml of a 1.7 mol L solution in hexane, 7.93 mmol) dropwise, and the resultant suspension stirred for 0.5 h. To this was added [2R*,4S*,5S*,6S*]-4,5-epoxy-2-methyl-1,7-dioxaspiro[5.5]undecane (1) (126 mg, 0.68 mmol) via a closed solid addition tube, the suspension allowed to warm to room temperature and stirred for an additional 16 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 were washed with water (20 ml) and dried over sodium sulphate. Removal of the solvent under reduced pressure gave an orange oil, that was purified by flash chromatography using hexane-ethyl acetate (6:4) as eluent to afford [2R*,5S*,6S*]-2-Methyl-1,7-dioxaspiro[5.5]undec-3-en-5-ol (2, 80 mg, 63%) as colourless needles [2].
M.p. 82-83 deg.C.
IR (Nujol) cm-1 3640-3200 (br, s, OH), 1650 (w, C=C), 1019 (C-O), 890 (m, C-O).
1H-NMR (400 MHz, CDCl3) 1.28 (3H, d, JMe,2 7.0 Hz, Me), 1.47-2.04 (7H, m, 9-CH2, 10-CH2, 11-CH2 and OH), 3.51 (1H, dd, J5,4 5.0 and J5,3 1.8 Hz, 5-H), 3.67 (1H, ddd, J8ax,8eq 11.2, J8ax,9ax 11.2 and J8ax,9eq 3.2 Hz, 8ax-H), 3.73-3.77 (1H, m, 8eq-H), 4.24 (1H, ddq, J2,Me 7.0, J2,3 3.4 and J2,4 1.5 Hz, 2-H), 5.84 (1H, dd, J3,4 10.2 and J3,2 3.4 Hz, 3-H), 5.91 (1H, ddd, J4,3 10.2, J4,5 5.0 and J4,2 1.5 Hz, 4-H).
13C-NMR (100 MHz, CDCl3) 18.3, 25.0, 30.8 (CH2, C-9, C-10 and C-11), 20.5 (CH3, Me), 62.9 (CH2, C-8), 64.6 (CH, C-2), 66.6 (CH, C-5), 97.1 (quat, C-6), 124.2, 133.8 (C-3 and C-4).
CI-MS 185, (M+H, 40%), 167 (M+H-H2O, 100), 101 (50), 84 (20).
Anal. calc. for C10H16O3 C, 65.11; H, 8.56%, M+H (CI, NH3) 185.1180 found C, 65.20; H, 8.75%; M+H, 185.1177.

Supplementary materials

Supplementary File 1Supplementary File 2

Acknowledgment 

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

References and Notes

  1. Crandall, J. K. Org. React. 1983, 346.
  2. Brimble, M. A.; Johnston, A. D. Another product (3, a colourless oil, 20 mg, 16%) will be reported in the following short note. Molecules 1997, 2, M16. [Google Scholar] [CrossRef]
  • Sample Availability: Available from MDPI, MDPI 11861.
Table
Table 1:. Product ratios for allylic and homoallylic alcohols (2) and (3).
Table 1:. Product ratios for allylic and homoallylic alcohols (2) and (3).
EpoxideSolventProduct Ratio
Allylic: Homoallylic		Overall Yield
1THF 1.0 : 1.373%
1Ether/Hexane (2:1) 1.4 :1.074%
1Hexane 4.0 : 1.079%

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MDPI and ACS Style

Brimble, M.A.; Johnston, A.D. [2R*,5S*,6S*]-2-Methyl-1,7-dioxaspiro[5.5]undec-3-en-5-ol§. Molecules 1997, 2, M15. https://doi.org/10.3390/M15

AMA Style

Brimble MA, Johnston AD. [2R*,5S*,6S*]-2-Methyl-1,7-dioxaspiro[5.5]undec-3-en-5-ol§. Molecules. 1997; 2(6):M15. https://doi.org/10.3390/M15

Chicago/Turabian Style

Brimble, Margaret A., and Andrew D. Johnston. 1997. "[2R*,5S*,6S*]-2-Methyl-1,7-dioxaspiro[5.5]undec-3-en-5-ol§" Molecules 2, no. 6: M15. https://doi.org/10.3390/M15

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