Iterative Arylation of Itaconimides with Diazonium Salts through Electrophilic Palladium Catalysis: Divergent β-H-Elimination Pathways in Repetitive Matsuda–Heck Reactions

Abstract

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Benign Arylations of Dimethyl Itaconate via Heck–Matsuda Reaction Utilizing in‐Situ Generated Palladium on Aluminum Oxide

“…Stimulated by the work of Correia and co‐workers concerning the biarylation of acrylates and maleic anhydride, the iterative Heck–Matsuda couplings with itaconimides by B. Schmidt et al and encouraged by our studies regarding the β,β‐diarylation of acrylates and vinylphosphonates we decided to embark on the biarylation of dimethyl iatconate. In accordance with our previous reaction conditions regarding the β,β‐diarylation of acrylates with palladium on aluminum phosphate as catalyst, we converted several diazonium salts (2.2 equiv.)…”

“…Thus, Correia and co‐workers already observed a similar kind of isomerization in the Heck–Matsuda reaction of methyl methacrylate and 4‐methoxybenzenediazonium salt, which gave a 1:1 ratio of constitutional isomers . Furthermore, B. Schmidt and colleagues observed corresponding isomerizations during the iterative Heck–Matsuda coupling of itaconimide and discussed various migration mechanisms in this context . In principle, the occurrence of the respective regioisomers should be explained by a respective kinetic or thermodynamic control.…”

“…Schmidt and colleagues recently described the successful arylation of itaconimides using the Heck–Matsuda reaction. With a catalyst concentration of 5 mol‐% the synthesis of 3‐arylmethylidene pyrrolidine‐2,5‐diones in good to very good yields was achieved …”

A Review on the Synthesis and Applications of α‐Alkylidene Succinimides

“…The mono aryl methylidene succinimides gave good yields for all substitution variations (Scheme 38). [66] However, 2‐NO 2 substituted diazonium salts failed to give the desired compound. In the case of di aryl methylidene succinimides 38 a , p‐acetyl and p ‐methoxy substituted arene diazonium salt were not compatible with the current reaction conditions.…”

Synthesis of Arylidene-β-lactams via exo-Selective Matsuda-Heck Arylation of Methylene-β-lactams

“…In continuation of previous studies from our group , on Heck reactions of exo -methylene-substituted heterocycles with arene diazonium salts (often named Matsuda-Heck reactions − ), we investigated the feasibility of this approach for the regio- and stereoselective synthesis of arylidene-β-lactams. The results are disclosed herein.…”