A Computational Study of the Hofmann Elimination Pathway for the MoritaBaylis-Hillman Reaction Under DABCO Catalysis. Participation of a Bridge-Head Ylide

15 April 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


In comparison to the popular pathway involving proton-transfer via a four-centred cyclic transition state structure, the recently proposed overall lower energy pathway involving proton-transfer via a seven-centred cyclic transition state structure followed by Hofmann elimination for the Me3N-catalyzed Morita-Baylis-Hillman reaction is applicable to the DABCO-catalyzed reaction equally well. This finding clearly establishes that the zwitterion at the bridge-head in DABCO is well tolerated. Also, the activation free energy of the rate-limiting aldol reaction under DABCO-catalysis is lower than that under Me3N-catalysis, suggesting that DABCO is likely a better catalyst to achieve faster conversion.


Morita-Baylis-HIllman reaction
Hofmann elimination
bridge-head ylide participation

Supplementary materials



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