Switchable Palladium-Catalyst Reaction of Bromomethyl Sulfoxides, CO, and N-Nucleophiles: Aminocarbonylation at Csp³ versus Oxidative Carbonylation of Amines

Abstract

The palladium-catalyzed reaction of α-bromomethyl sulfoxides, carbon monoxide, and N-nucleophiles follows different reaction pathways according to the catalytic system and the reaction conditions. The Pd-xantphos catalyst affords high yields of α-sulfinyl amides by an aminocarbonylation process and is the first example of this type of transformation for a nonbenzylic sp(3)-hybridized carbon. On the other hand, the oxidative carbonylation of amines occurs with α-bromomethyl sulfoxides, carbon monoxide, and catalytic Pd(PPh(3))(4) under aerobic conditions, yielding ureas and oxalamides from either primary or secondary amines. The reaction with ambident nucleophiles such as amino alcohols was highly selective and took place exclusively at the amino group despite the presence of the alcohol functionality. In parallel to the reaction paths for simple amines, amino alcohols were converted into hydroxy sulfinyl amides when the reaction was catalyzed by Pd-xantphos, while Pd(PPh(3))(4) catalyst afforded cyclic carbamates. The alkoxycarbonylation reaction of bromomethyl sulfoxides with simple alcohols and CO leading to the corresponding sulfinyl esters is also described.

Binary Polyazides of Cadmium and Mercury

“…The usual reaction sequence in Suzuki carbonylative reactions between aryl halides and boronic acids, namely, oxidative addition, CO coordination followed by aryl migration and then transmetallation of the resulting acylpalladium(II) complex, hardly explains our previous findings in the palladium‐catalyzed carbonylative Suzuki reaction of bromomethyl sulfoxides. With these compounds as electrophiles the insertion of carbon monoxide takes place after the transmetallation step 21. Halomethyl oxime ethers also contain an electron‐withdrawing substituent in the α‐position relative to the halide.…”

Transamidation of Carboxamides Catalyzed by Fe(III) and Water

“…Mp: 170 °C (lit. 23 170−171 °C). 1 H NMR (300 MHz, DMSO): δ (ppm) 7.02−7.51 (m, 10H), 6.45 (t, J = 5.9 Hz, 2H), 4.25 (d, J = 6.0 Hz, 4H).…”