443146-48-3Relevant academic research and scientific papers
SN2' versus SN2 reactivity: Control of regioselectivity in conversions of Baylis-Hillman adducts
Baidya, Mahiuddin,Remennikov, Grygoriy Y.,Mayer, Peter,Mayr, Herbert
supporting information; experimental part, p. 1365 - 1371 (2010/06/14)
TiCl4-induced Baylis-Hillman reactions of α,β- unsaturated carbonyl compounds with aldehydes yield the (Z)-2-(chloromethyl) vinyl carbonyl compounds 5, which react with 1,4diazabicyclo[2.2.2]octane (DABCO), quinuclidine, and pyridines to give the allylammonium ions 6. Their combination with less than one equivalent of the potassium salts of stabilized carbanions (e.g. malonate) yields methylene derivatives 8 under kinetically controlled conditions (SN2' reactions). When more than one equivalent of the carbanions is used, a second SN2' reaction converts 8 into their thermodynamically more stable allyl isomers 9. The second-order rate constants for the reactions of 6 with carbanions have been determined photometrically inDMSO. With these rate constants and the previously reported nucleophilespecific parameters N and s for the stabilized carbanions, the correlation log k (20°C) = s(N + E) allowed us to calculate the electrophilicity parameters E for the allylammonium ions 6 (-19 a rate-determining addition step.
