Ketones arylation reactions

Complex 7 was tested for a-ketone arylation reactions (Table 14.9) and Bnchwald-Hartwig ami-nation reactions with activated and unactivated aryl chlorides (Table 14.10). In both cases, very good results were obtained using mild temperatures in short reaction times. 

A limited number of studies focussed on the development of NHC-Pd catalysts for polymerisation reactions. The a-ketone arylation reactions, described in Section 9.2.8, can be applied to the polycondensation of haloarylketones. Thus, Matsubara reported the polymerisation of bromo- or chloro-propiophenone catalysed by mixtures of [Pd(OAc)2] and IPr HCl or IMes HCl (3 mol% [Pd]). The former system was more active and the use of excess imidazolium salts resulted in decreased activity, due to the formation of bis-NHC Pd species. Chung reported the application of Nolan-type Pd-allyl catalysts (see Figure 9.8) to the polymerisation of ester-functionalised norbornene monomers. " These substrates are typically more difficult to polymerize than non-functionalised monomers, and such catalysts efficiently catalysed the polymerisation of simple... 

Another arylation reaction which uses arenediazonium salts as reagents and is catalyzed by copper should be discussed in this section on Meerwein reactions. It is the Beech reaction (Scheme 10-49) in which ketoximes such as formaldoxime (10.13, R=H), acetaldoxime (10.13, R=CH3), and other ketoximes with aliphatic residues R are arylated (Beech, 1954). The primary products are arylated oximes (10.14) yielding a-arylated aldehydes (10.15, R=H) or ketones (10.15, R=alkyl). Obviously the C=N group of these oximes reacts like a C = C group in classical Meerwein reactions. It is interesting that the addition of some sodium sulfite is necessary for the Beech reaction (0.1 to 0.2 equivalent of CuS04 and 0.03 equivalent of Na2S03). 

Ketones, coupling reactions of aryl halides with, 487-489 k-factor, 244 Kinetic studies, 73 Kumada coupling, 467, 489, 491... 

In addition to aryl halides and triflates, organometallic reagents can be utilized for the catalytic arylation reaction. The rhodium-catalyzed arylation of arylpyridines proceeds with the use of tetraarylstannanes (Equation (67)).83 The ruthenium-catalyzed reaction of aromatic ketones with arylboronates affords the ortho-arylated aromatic ketones (Equation (68)).84... 

Carbonylation of halides with tetramethyltin This nickel complex is the most efficient catalyst for the synthesis of methyl ketones by reaction of aryl halides with carbon monoxide and tetramethyltin in HMPT at 120°. No reaction occurs when tetraphenyltin is used. A typical reaction is formulated in equation (I). 

With unsymmetrical methyl ketones arylation occurred at the primary carbon. Where two yields are stated the figure in parentheses is the isolated yield and the other is analytical (e.g. determined by GLC or H NMR). Reaction in the dark, catalyzed by iron(II) sulfate. dBoth halogens replaced. 

Buchwald has designed a hindered dialkylphosphino-binaphthyl ligand (3) that is much more active than the original ligand for asymmetric arylation of ketone enolates. Reactions occur at room temperature using only 2 mol % catalyst with enantioselectivities up to 94% [41]. Additionally, the Buchwald group has developed an electron-rich monodentate ligand (4) capable of vinylation of ketone enolates with up to 92% ee [42]. 

Aromatic ketones arylations, 10, 140 asymmetric hydrogenation, 10, 50 G—H bond alkylation, 10, 214 dialkylzinc additions, 9, 114-115 Aromatic ligands mercuration, 2, 430 in mercury 7t-complexes, 2, 449 /13-77-Aromatic nitriles, preparation, 6, 265 Aromatic nucleophilic substitution reactions, arene chromium tricarbonyls, 5, 234... 

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