Morita–Baylis–Hillman Reaction of <i>N</i> ‐Aryl Acrylamide, with a Vast Substrate Scope: Importance of <i>N</i> H Proton in Reaction Mechanism

The Morita–Baylis–Hillman (MBH) reaction involves the coupling of a Michael acceptor with an electrophile. The MBH adduct is a heavily decorated synthetic template with numerous applications. Unfortunately, acrylamide, being a fundamental Michael acceptor, has been left out of the MBH domain. With limited reports or indirect methods to access acrylamide‐derived MBH adducts, their further applications remain unexplored. Herein, we report the MBH reaction of N ‐aryl acrylamide with an unprecedented substrate scope. Extensive optimisations were carried out. For substrate scope, wide‐ranging variations were successfully carried out at the aldehyde and acrylamide ends. Additives in the form of protecting groups and functional groups were also evaluated effectively. The reactions were conducted, mostly in solvent‐free conditions, making it a green protocol. With control experiments, we also uncover the vital role that the N  H proton plays for proton transfer and rate acceleration in the reaction mechanism.