(E)-3-Arylidene-4-diazopyrrolidine-2,5-diones: Preparation and Use in RhII-Catalyzed X–H Insertion Reactions towards Novel, Medicinally Important Michael Acceptors

Abstract

The use of readily available 1-aryl-3-arylidenepyrrolidine-2,5-diones in high yielding direct diazo-transfer reactions and subsequent involvement of the resulting diazo compounds in RhII-catalyzed O–H, S–H, and N–H insertion reactions delivered 4-substituted 1-aryl-3-arylidenepyrrolidine-2,5-diones of defined regiochemistry and geometrical configuration. These products are intended to be studied as Michael acceptors capable of inhibiting thioredoxin reductase, a promising cancer target.

Diazo Glutaconimides: an Unexplored Type of Heterocyclic α‐Diazocarbonyl Compounds Conveniently Evolved into Pyridine‐2,6(1H,3H)‐diones and Oxazolo[5,4‐b]pyridin‐5(4H)‐ones

“…[13] Continuing this line of inquiry, diazo barbituric acids 2 were successfully prepared and involved in the preparation of biologically relevant oxazolo [5,4-d]pyrimidine-5,7-diones via Rh (II)-catalyzed condensation with nitriles. [14] Most recently, we [15] and others [16] introduced (E)-3-arylidene-4-diazopyrrolidine-2,5diones 3 also prepared via direct diazo transfer to readily available 3-arylidene pyrrolidine-2,5-diones. Compounds 3 have been shown to undergo metal carbene-mediated XÀ H insertion reactions [15] and [2 + 1] cycloaddition with aldehydes; [16] their synthetic potential continues being unraveled in our laboratories.…”

“…[14] Most recently, we [15] and others [16] introduced (E)-3-arylidene-4-diazopyrrolidine-2,5diones 3 also prepared via direct diazo transfer to readily available 3-arylidene pyrrolidine-2,5-diones. Compounds 3 have been shown to undergo metal carbene-mediated XÀ H insertion reactions [15] and [2 + 1] cycloaddition with aldehydes; [16] their synthetic potential continues being unraveled in our laboratories. [17] Recently we developed the synthesis of 3arylpent-2-enedioic (β-arylglutaconic) acids [18] and successfully employed them and their anhydrides in various multicomponent transformations.…”

Access to 3-Aminomethylated Maleimides via a Phosphine-Catalyzed Aza-Morita–Baylis–Hillman Type Coupling

“…For example, Hedaya and Theodoropulos published a reliable method to generate stable phosphorus ylide from triphenylphosphine and maleimides . Through a second Michael-addition intermolecular substitution mode, the prepared ylide shows its application in Morita–Baylis–Hillman (MBH) reactions (Scheme , c) . As for phosphine mediated aza-MBH reactions where imines serve as an electrophile, many protocols adopt an auxiliary sulfone or carbonyl group for promoting the transformation.…”