A relationship between the catalytic carbonylation of (N-arenesulfonyl)imides and iodonium ylides

Abstract

Reactivities of various sulfonamide derivatives of general formula ArSO 2 N=XPh n (X = I; n = 1; X = S, Se, n = 2; X = P, As, n = 3) in catalytic carbonylations have been explained by structural properties of the substrates. Based on crystallographic data reported in the literature, it has been concluded that the two-step catalytic oxidative carbonylation of sulfonylimides proceeds only when the N=X double bond is strongly polarized. The structural requirement observed within the sulfonamide derivatives has been found to be applicable for iodonium ylides. Catalytic carbonylation of the phenyliodonium methylide (3a) prepared from dimedone (5,5-dimethyl-1,3-cyclohexanedione) and (diacetoxyiodo)benzene, resulted in a new spirobenzofuranone derivative (5a) which was characterized by X-ray single crystal diffraction, 1 J C,C coupling constants, 13 C-T 1 relaxation times, as well as by IR and Raman spectroscopic methods. Crystals of 5a are monoclinic, space group P2 1 /c, a = 7.187 (1), b = 21.129(1), and c = 10.636(1) Å, β = 92.81(1)°, V = 1613.2(3) Å 3 , and Z = 4. A ketene intermediate has been postulated in the catalytic carbonylation of the iodonium ylide. A survey of databases has revealed that the triacyl dihydrofuranone moiety in 5a constitutes a new structural unit.Résumé : Les réactivités de divers dérivés du sulfonamide, de formule générale ArSO 2 N=XPh n (X = I, n = 1; X = S, Se, n = 2; X = P, As, n = 3), dans des réactions de carbonylations catalytiques sont expliquées par des propriétés structurales des substrats. En se basant sur des données cristallographiques rapportées dans la littérature, on a conclu que la réaction de carbonylation oxydante, catalysée et en deux étapes, de sulfonylimides ne se produit que lorsque la double liaison N=X est fortement polarisée. On a trouvé que les conditions structurales observées dans les dérivés sulfonamides s'appliquent aussi aux ylures d'iodonium. La carbonylation catalytique du méthylure de phényliodonium (3a) préparé à partir de la dimédone (5,5-diméthylcyclohexane-1,3-dione) et de (diacétoxyiodo)benzène, conduit à la formation d'un nouveau dérivé spirobenzofuranone (5a) qui a été caractérisé par diffraction des rayons X sur un cristal unique, par les constantes de couplage 1 J C,C , les temps de relaxation 13 C-T 1 ainsi que par spectroscopies IR et Raman. Les cristaux de 5a sont monoclinique, groupe d'espace P2 1 /c avec a = 7,187(1), b = 21,129(1) et c = 10,636(1) Å, β = 92,81°, V = 1613,2(3) Å 3 et Z = 4. On suggère l'existence d'un intermédiaire cétène lors de la carbonylation catalytique de l'ylure d'iodonium. Une revue des bases de données indique que la partie triacyldihydrofuranone du composé 5a correspond à une nouvelle unité structurale.

Lewis Acid-Catalyzed [3 + 2]-Cyclization of Iodonium Ylides with Azadienes: Access to Spiro[benzofuran-2,2′-furan]-3-ones

“…However, iodonium ylide in constructing structurally various spiroheterocycles is still in its infancy. Only one procedure was reported on a palladium-catalyzed oxidative carbonylation of 4,4-dimethyl-2,6-dioxocyclohexylides to provide the spirobenzofuranones by Besenyei and co-workers (Scheme , c), which limited by the narrow scope of substrates . Based on our research on the construction of heterocyclic compounds, herein, we disclosed a Lewis acid-catalyzed [3 + 2] cyclization of iodonium ylides with benzofuran-derived azadienes (BDAs) to afford spiro­[benzofuran-2,2′-furan]-3-ones with high stereoselectivity (Scheme , d).…”

The Question of Electrophilic vs Nucleophilic Addition of Cyclic β-Dicarbonyl Phenyliodonium Ylides: Electrophilic Cycloaddition of Diphenylketene

“…This was explained as a consequence of a formal 1,3-addition of phenyliodonium ylide 2f on diphenylketene. On the other hand, a similar aurone derivative was isolated upon catalytic carbonylation of iodonium ylide 2f via the intermediate ketene, which was thought to be the primary unstable product of the carbonylation reaction.…”