Determining Michael Acceptor Reactivity from Kinetic, Mechanistic, and Computational Analysis for the Base-catalyzed Thiol-Michael Reaction.

ABSTRACT: A combined experimental and computational study of the reactivities of seven commonly used Michael acceptors paired with two thiols within the framework of photobase-catalyzed thiol-Michael reactions is reported. The rate coefficients of the propagation (k_P), reverse propagation (k_-P), chain-transfer (k_CT), and overall reaction (k_overall) were experimentally determined and compared with the well-accepted electrophilicity parameters of Mayr and Parr, and DFT-calculated energetics. Both Mayr's and Parr's electrophilicity parameters predict the reactivities of these structurally varying vinyl functional groups well, covering a range of overall reaction rate coefficients from 0.5 to 6.2 s^-1. To gain insight into the individual steps, the r

SUBMITTER: Huang S 

PROVIDER: S-EPMC8409055 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature