An experimental investigation into the kinetics and mechanism of the aza-Michael additions of dimethyl itaconate

TY - JOUR

T1 - An experimental investigation into the kinetics and mechanism of the aza-Michael additions of dimethyl itaconate

AU - Day, Dan

AU - Farmer, Thomas James

AU - Sherwood, James Richard

AU - Clark, James Hanley

N1 - © 2022 The Author(s).

PY - 2022/8/17

Y1 - 2022/8/17

N2 - The aza-Michael addition is a versatile reaction for the modification of α,β-unsaturated carbonyl compounds with amines. The reactivity of dimethyl itaconate as a bio-based Michael acceptor is explored in this work. Through its reactions with piperidine and dibutylamine, it was found that the order of reaction can be changed by the choice of catalyst, solvent, or the concentration of the amine reactant. The effectiveness of catalysts was proportional to their Lewis acidity. Competitive isomerisation of dimethyl itaconate into unreactive regioisomers can be suppressed using low-polarity solvents and lower temperatures. This investigation of the aza-Michael additions of dimethyl itaconate has clarified the possible reaction mechanisms and optimised the protocol, supporting further use of this reaction in small molecule synthesis and modification of polymers.

AB - The aza-Michael addition is a versatile reaction for the modification of α,β-unsaturated carbonyl compounds with amines. The reactivity of dimethyl itaconate as a bio-based Michael acceptor is explored in this work. Through its reactions with piperidine and dibutylamine, it was found that the order of reaction can be changed by the choice of catalyst, solvent, or the concentration of the amine reactant. The effectiveness of catalysts was proportional to their Lewis acidity. Competitive isomerisation of dimethyl itaconate into unreactive regioisomers can be suppressed using low-polarity solvents and lower temperatures. This investigation of the aza-Michael additions of dimethyl itaconate has clarified the possible reaction mechanisms and optimised the protocol, supporting further use of this reaction in small molecule synthesis and modification of polymers.

U2 - 10.1016/j.tet.2022.132921

DO - 10.1016/j.tet.2022.132921

M3 - Article

SN - 0040-4020

VL - 121

JO - Tetrahedron

JF - Tetrahedron

M1 - 132921

ER -