Palladium-catalyzed carbonylative domino reactions

2 Transition-Metal-CatalYzed Carbonylative Domino Reactions 119 pd) O 

In 2000, a palladium-catalyzed decarboxylative carbonylation of 5-vinyloxazolidin-2-ones was studied by Knight and coworkers [44]. By a palladium-catalyzed decarboxylative carbonylation process, 5-vinyloxazohdin-2-ones, which are prepared 

Recently, an efSdent method for the synthesis of 1,4-benzo- and pyrido-oxazepinones was also disdosed [46]. This reaction proceeds via a domino process through one-pot ring-opening/carboxamidation reaction sequences of N-tosylaziri-dines with 2-halophenols/pyridinol under phase-transfer conditions (benzyltriethy-lammonium chloride, TEBA). A variety of 1,4-benzo- and pyrido-oxazepinones 

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In summary, we have summarized representative examples of transition-metal-catalyzed carbonylative domino reactions. In the area of carbonylations, palladium, rhodium, and cobalt are still the main actors. The abihty of palladium catalysts in carbonylative cross-coupling, rhodium catalysts in carbonylative C-H activation, and cobalt catalyst in carbonylative reactions with unsaturated bonds is impressive. 

A 2009 paper described a palladium-catalyzed domino-C,N-coupling/carbonyl-ation/Suzuki coupling reaction was used provide an efficient synthesis of 2-aroyl-/ heteroaroylindoles [163]. For instance, 2-ge/M-dibromovinyIaniline 118 and 3-furyl-boronic acid under carbon monoxide afforded 3-fuiylindole 119 in 67% yield. 

The palladium(II)-catalyzed olefin carbonylation reaction was first reported more than 30 years ago in studies by Stille and co-workers and James et al. The reaction of carbon monoxide with cis- and tra 5-but-2-ene in methanol in the presence of palladium(II)-chloride and copper(II)-chloride yielded threo- and eryt/zro-3-methoxy-2-methyl-butanoate, respectively. The transformation that was based on the well-known Wacker process for oxidation of ethylene into acetaldehyde in water " is now broadly defined as the Pd(II)-catalyzed oxycarbonylation of the unsaturated carbon-carbon bonds. This domino reaction includes oxypalladation of alkenes, migratory insertion of carbon monoxide, and alkoxylation. Since the development of this process, several transformations mediated by palladium(II) compounds have been described. The direct oxidative bisfunctionalization of alkenes represents a powerful transformation in the field of chemical synthesis. Palladium(II)-promoted carbonylation of alkenes in the presence of water/alcohol may lead to alkyl carboxylic acids (hydrocarboxylation), diesters [bis(aIkoxycarbonyla-tion)], (3-alkoxy carboxylic acids (alkoxy-carboxylation), or (3-alkoxy esters (alkoxy-carbonylation or alkoxy-alkoxy-carbonylation). Particularly attractive features of these multitransformation processes include the following ... 

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