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Copyright Syntheticpages 2001




Organolithium-Induced Synthesis of Unsaturated Diols from Epoxides of Dihydrofurans and Dihydropyrans; 4-(Trimethylsilyl)-3-methylenebutane-1,2-diol

SyntheticPage 196 (2002)
Submitted 25th Mar 2002, published 26th Mar 2002

Matthew Stent (matthew.stent@chem.ox.ac.uk),
A contribution from the Hodgson Group, Oxford


Reaction Scheme

Chemicals Used
3,4-Epoxytetrahydrofuran (Tetrahedron, 1993, 49, 6263-6276) (Trimethylsilyl)methyllithium (1.0 M in pentane, Aldrich) Tetrahydrofuran (distilled from sodium benzophenone)

Procedure
A solution of 3,4-epoxytetrahydrofuran (80 mg, 930 mmol) in THF (5 mL) cooled to 78 °C is treated dropwise with TMSCH2Li (2.3 mL, 2.3 mmol, 2.5 eq.). After stirring at 78 °C for 1 h and then at 25 °C for 1 h, phosphate buffer (pH 7, 5 mL) was added. The mixture was extracted with EtOAc (2 x 10 mL), the combined organic layers dried (MgSO4), filtered and concentrated under reduced pressure. Purification of the residue by column chromatography (SiO2, 3 : 1 Et2O : 40 - 60 °C petrol) gave the product as a colourless oil (0.12 g, 73%).

Author's Comments
For optimal yields both the epoxide (distillation, boiling point: 65 °C / 45 mmHg) and THF need to rigorously dried prior to use, all glassware should be flame dried and needles and syringes should be purged with argon. Analogous procedures have been successfully conducted on up to a 5 mmol scale with no reduction in yield.

Data
Rf 0.25 (3 : 1 Et2O : 40 - 60 °C petrol). 1H NMR (400 MHz, CDCl3) 4.83 (s, 1 H, C=CH2), 4.59 (s, 1 H, C=CH2), 3.91 - 3.86 (m, 1 H, C(2)-H), 3.57 - 3.50 (m, 1 H, C(1)-H), 3.34 - 3.20 (m, 3 H, C(1)-H and 2 x OH), 1.46 (d, 1 H, J = 14.0 Hz, C(4)-H), 1.21 (d, 1 H, J = 14.0 Hz, C(4)-H), 0.12 (s, 9 H, TMS). 13C NMR (100 MHz, CDCl3) 146.0 (C(3)), 108.2 (C=CH2), 75.6 (C(2)), 65.5 (C(1)), 23.3 (C(4)), 1.5 (TMS).


Lead Reference
D. M. Hodgson, M. A. H. Stent and F. X. Wilson, Org. Lett., 2001, 3401 3403.

Other References

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SyntheticPagesTM are for use exclusively by those with training and experience in synthetic chemistry. While contributors are asked to identify hazards and to use methods designed to reduce risk, no formal hazard or risk assessments are included, and these procedures must be conducted at one's own risk. SyntheticPages, its editors, owners and associates do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein. Copyright ©2005 Synthetic Pages

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