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Topic: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction  (Read 1412 times)

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Offline Babcock_Hall

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We have used Masamune-Roush conditions in Horner Wadsworth Emmons reactions with good results on a number of occasions.  Last week we had a rare failure using 5-nitrofuraldehyde and diethyl methylsulfonylmethylphosphonate, with DBU as the base.  So far the only product that I have identified by NMR is the phosphonate starting material.  There may be some aldehyde remaining.  TLC with UV detection showed many spots, some of which faded with time.

Does this furan have a propensity to react in other ways?  I am told it may do single electron chemistry, but I don't have a reference for this.  If we substituted the corresponding thiophene for this furan, are we likely to do any better?  Thanks for any ideas.
« Last Edit: January 25, 2023, 07:36:07 PM by Babcock_Hall »

Offline Babcock_Hall

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Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
« Reply #1 on: January 26, 2023, 10:17:45 AM »
One more modest point of interest.  The darkness of the color waxed and waned over the fractions.  Yet, the first two pools that we analyzed by H-1 NMR were nearly pure diethyl methylsulfonylmethylphosphonate, the colorless starting material.

Offline Babcock_Hall

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Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
« Reply #2 on: January 26, 2023, 10:19:32 PM »
Furan is weakly aromatic, and thiophene is strongly aromatic.  That may tip the balance in favor of a Horner reaction with respect to thiophene.

Offline Babcock_Hall

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Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
« Reply #3 on: February 09, 2023, 11:48:15 AM »
The corresponding thiophene-based aldehyde gave a more typical reaction and was purified with little difficulty.  Although there was at least one other product, it moved much more slowly through the silica column, and we have not attempted to isolate it.

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