The thia-Michael reaction, i.e., the addition of a thiol to an α,β-unsaturated carbonyl moiety, has recently gained significant attention within the field of dynamic covalent chemistry. Interestingly, including an additional electron-withdrawing group at the α-position of the Michael acceptor can result in room temperature (rt), catalyst-free dynamic thia-Michael reactions. Importantly, the electronic nature of the Michael acceptor can be used to tune the equilibrium constant (