Stereoselective Preparation of Deuteriated Dienes by Ring Fragmentation of Metallated Cyclopropylcarbinols

Abstract

The hydroalumination reaction of cyclopropenylcarbinols initially leads to the alumino-cyclopropylcarbinol derivatives, which is followed by an elimination reaction to give the corresponding substituted dienes as unique isomers and in good yields. The use of LiAlD₄ as reducing agent provides stereoselectively substituted deuteriodienes.

Key words

dienes - deuteriodienes - reducing agent - cyclopropane - cyclopropene

References

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17

General Procedure for the Preparation of Dienes from Cyclopropenylcarbinols 1a-g: LiAlH₄ (or LiAlD₄, 1 M solution in Et₂O, 1 mmol) was added to a stirred solution of 1a-g (1 mmol) in 5 mL of benzene at 5 °C. The reaction mixture was then heated to 80 °C for several hours and the sequential reduction and elimination reactions were followed by TLC. When the transformation was complete, 1 M aq solution of HCl (3 mL) was added and the aqueous layer was extracted with Et₂O (3 × 5 mL). The combined organic phases were dried over MgSO₄, filtered and the solvent was removed under reduced pressure. Chromatography on silica gel (eluent: hexane) gave the dienes 4a-k in yields indicated in Table [1] .