Ketones synthesis from acid chlorides and

Milstein, D., Stille, J. K. A general, selective, and facile method for ketone synthesis from acid chlorides and organotin compounds catalyzed by palladium. J. Am. Chem. Soc. 1978,100, 3636-3638. 

Related to the original Suzuki coupling is the ketone synthesis from acid chloride and trialkyl boranes and thiol esters with arylboronic acids. - The latter procedure is Pd-catalyzed and Cu-mediated. 

D. Milstein and J. K. Stille, General, Selective, and Facile Method for Ketone Synthesis from Acid-Chlorides and Organotin Compounds Catalyzed by Palladium,/. Am. Chem. Soc, 1978,100(11), 3636-3638. 

Synthesis of Aldehydes and Ketones from Acid Chlorides and Esters 835... 

Methyl ketonesfrom carboxylic acid chlorides (3,112). Posner e/n/. report that the synthesis of ketones from acid chlorides and organocopper reagents is applicable to acid chlorides containing iodo, cyano, acyl, and carboalkoxy groups. The reaction, however,... 

O. R. 1-9, C. R. Hauser and B. E. Hudson, Jr., The Acctoacetic Ester Condensation and Related Reactions lV-4, S. M. McElvain, The Acyloins 11-4, W. S. Johnson, The Formation of Cyclic Ketones by Intramolecular Acylation VIII-2, D. A. Shirley, The Synthesis of Ketones from Acid Chlorides and Organometallic Compounds of Magnesium, Zinc, and Cadmium. ... 

Dialkylzinc is another common substrate in Pd-catalyzed couplings. An efficient ketone synthesis uses acid chlorides as starting material (Scheme 1-9). The use of PdCl2(dppf) offers high yields and is best in restricting the formation of benzaldehyde as a )8-elimination byproduct [117]. A-Aryl aromatic imine 34 can be obtained from aromatic iodides and aryl isocyanide 35 [118]. The proposed intermediate,... 

The most general methods for the syntheses of 1,2-difunctional molecules are based on the oxidation of carbon-carbon multiple bonds (p. 117) and the opening of oxiranes by hetero atoms (p. 123fl.). There exist, however, also a few useful reactions in which an a - and a d -synthon or two r -synthons are combined. The classical polar reaction is the addition of cyanide anion to carbonyl groups, which leads to a-hydroxynitriles (cyanohydrins). It is used, for example, in Strecker s synthesis of amino acids and in the homologization of monosaccharides. The ff-hydroxy group of a nitrile can be easily substituted by various nucleophiles, the nitrile can be solvolyzed or reduced. Therefore a large variety of terminal difunctional molecules with one additional carbon atom can be made. Equally versatile are a-methylsulfinyl ketones (H.G. Hauthal, 1971 T. Durst, 1979 O. DeLucchi, 1991), which are available from acid chlorides or esters and the dimsyl anion. Carbanions of these compounds can also be used for the synthesis of 1,4-dicarbonyl compounds (p. 65f.). 

Mixed homocuprates.7 Mixed cuprates (1) in which the nontransferable ligand is an a-sulfonyl carbanion are easily prepared from dimethyl sulfone or methyl phenyl sulfone (equation I), and are effective for conjugate addition to enones and for a synthesis of ketones from acid chlorides. 

A study of the Staudinger synthesis of /3-lactams from a diazo ketone, an acid chloride, and an imine (under basic conditions) has explored the cis/trans selectivity as a function of time, temperature, solvent, and the order of addition of reagents.81... 

As outlined in Scheme 28, the synthesis of the P-ketophosphonate 131 began with a one-pot anh -aldol/reduction step between ethyl ketone 101 and aldehyde 133, giving the 1,3-syn diol 134 (>30 ldr) [130, 132-136, 145, 146], The diol 134 was then converted into the carboxylic acid 135 in six steps. Completion of the subunit 131 required conversion into the acid chloride and reaction with the lithium anion of methyl-(di-l,l,l-trifluoroethyl)-phosphonate. The C9-C24 aldehyde 132 was prepared in two steps from 136, an intermediate from previous routes [55-58], The Still-Gennari-type coupling of 131 and 132 was readily achieved via treatment with... 

Synthesis from Acelyl Chloride.— As can be readily seen this is the simplest ketone acid that is possible and it is an alpha-V.tiont acid. Its name is derived from the fact that it is obtained from racemic acid by heat. It is a liquid boiling at 165°. Its constitution is best shown by the following syntheses. Acetyl chloride by means of silver cyanide yields acetyl cyanide which by hydrolysis gives pyro-racemic acid. 

The synthesis of ketones from acid chlorides has been demonstrated with several organometallic reagents (see Sections 1.13.3,1.13.4 and 1.13.5) however, the acylation of organolithiums often leads to substantid amounts of overaddition product. Initially, acid chlorides appear to be a poor choice for... 

The acyliron(0) complex (102) has been isolated and subjected to the same nucleophilic displacement (or equivalently oxidative addition) with excellent correlation (Scheme 39). The same species is also readily available from acid chlorides (i.e. formation of 103), but the overall process has not been widely used in the synthesis of ketones (Scheme 40). The final step of the process, a reductive elimination of acyliron(II) complex (104) or (105), is quite rapid and it has not been possible to isolate and identify the presumed intermediates in this case (Scheme 41). Since the oxidative addition of the acyliron complex with the alkyl halide is extremely mild, the corresponding ketone formed in the reaction is not subject to attack by organometallic reagents and no tertiary tdcohol is formed. 

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