A Convenient Method for the Synthesis of Terminal (E)-1,3-Dienes

Abstract

Lithiated allylic phosphonates undergo efficient olefination reactions with a variety of aldehydes in the presence of HMPA to give terminal 1,3-dienes with high selectivity for the E-isomer. This method is general and procedurally simple.

Key words

aldehydes - alkenation - phosphorus - Wittig reactions - ylides

References

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• 19a

  BuLi (1.2 equiv) was added to 5a and HMPA (2.4 equiv) in THF at -78 °C, and the solution was stirred for 1 h. Aldehyde 2 in THF was added dropwise and the reaction mixture was allowed to warm to r.t.; yield <20%.

• 19b

  BuLi (1.2 equiv) was added to 5a in THF at -78 °C, and the solution was stirred for 1 h. Aldehyde 2 and HMPA (2.4 equiv) in THF were added dropwise and the reaction mixture was allowed to warm to r.t.; yield: 42%.

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14

While this work was underway, Schlosser and Liu reported a highly stereoselective synthesis of (E)-1,3-dienes with allylphosphonates. [15] However, experimental details were not provided for the optimized conditions using unsubstituted diethyl allylphosphonate with the straight-chain aldehyde nonanal (NaH activated with LiAlH₄), and we could not consistently reproduce the reported results (74% yield, 99:1 E/Z).