Reaction Heck aminocarbonylation

The group also reported DME in the presence of potassium tert-butoxide to be an efhcient source of carbon monoxide and dimethyl-amine in palladium-catalyzed aminocarbonylation (Heck carbonylation Scheme 25.2D). The addition of excess amines to the reaction mixture provided good yields of the corresponding aryl amides. The reaction proceeded smoothly with bromobenzene and more electron-rich aryl bromides, but not with electron-deficient aryl bromides. 

The above solid catalysts were used successfully to catalyze various reactions, like the Suzuki-Miyura reaction [15], such as aminocarbonylation, amidatimi, and the Heck reactions [16]. Polymers containing scandium trillate, ruthenium, platinum, or gold were prepared to perform Mukayama aldol, alcohol, and sulfide oxidation, hydrogenatirMi, and indole syntheses [17]. 

More recently, a microwave-promoted palladium-catalyzed aminocarbonyla-tion of (hetero)aryl halides (X = I, Br, Cl) using Mo(CO)e and allylamine as a nucleophile was also described [190, 191]. Remarkably, no side products resulting from the competing Heck reaction were detected. Importantly, this was the achievement that aminocarbonylation was realized on a larger laboratory scale (25 mmol) starting from 4-iodoanisole (Scheme 2.18). 

Like alkoxycarbonylation, aminocarbonylation, and hydroxycarbonylation, the palladium-catalyzed reductive carbonylation reaction was originally discovered by Schoenberg and Heck in 1974 [15]. In the presence of a relatively large amount of [PdX2(PPh3)2l as a catalyst under 80-100 bar of synthesis gas and at 80-150 °C, aryl and vinyl bromides or iodides were converted into the corresponding aldehydes in good yields (Table 3.1). 

The Carbonylative Heck Reaction is not the same as those that were traditionally called Heck carbonylations . Heck carbonylations normally include alkoxycarbonylation, aminocarbonylation and hydroxycarbonylation, while a carbonylative Heck reaction is more related to a Heck reaction. In the late 1960s, Richard Heck developed several coupling reactions of arylmercury compounds in the presence of either stoichiometric or catalytic amounts of palladium salts [1-7]. Based on this work in 1972, he described a protocol for the coupling of iodo-benzene with styrene, which today is known as the Heck reaction [8]. In contrast to this, the catalytic insertion of olefins into acylpalladium complexes is called a Carbonylative Heck reaction . Here the acylpalladium complexes can either by CO insertion or by the oxidative addition of benzoyl precursors [9, 10]. 

Palladium bromide is also an efficient Pd(0) catalyst precursor for the aminocarbonylation of benzyl chlorides (eq 46), car-bonylative Heck reaction of aryl bromides with vinyl ethers (eq 47), and carbonylation of halogenoalkynes (eq 48). ... 

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