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Synthesis of aldehydes and ketones

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Weinreb Ketone Synthesis

Recent Literature

A range of unsymmetrical ketones has been prepared in good yields from aldehydes in one simple synthetic operation by addition of organolithium compounds followed by an oxidation using N-tert-butylphenylsulfinimidoyl chloride.
J. J. Crawford, K. W. Hederson, W. J. Kerr, Org. Lett., 2006, 8, 5073-5076.

The use of Zn powder in the presence of LiCl in THF allows a simple, high-yielding preparation of a broad range of functionalized aryl- and heteroarylzinc reagents. The synthesis of alkylzinc reagents was performed from inexpensive alkyl bromides.
A. Krasovski, V. Malakhov, A. Gavryushin, P. Knochel, Angew. Chem. Int. Ed., 2006, 45, 6040-6044.

A new Ni catalyst is capable of effecting the rapid cross-coupling of acid fluorides, acid chlorides, acyl cyanides, anhydrides, thioesters, and pyridyl esters with both groups of diorganozinc reagents. Reactions with acid fluorides as electrophilic partners tolerate epimerizable functionality as well as leaving groups.
Y. Zhang, T. Rovis, J. Am. Chem. Soc., 2004, 126, 15964-15965.

Tetraorganoindates, which are easily prepared from 1 eq. of InCl₃ and 4 eq. of organometallics, could be employed as effective nucleophilic cross-coupling partners in Pd-catalyzed carbonylative cross-coupling reactions with a variety of halides. The present method gave unsymmetrical ketones in good yields.
S. W. Lee, K. Lee, D. Seomoon, S. Kim, H. Kim, H. Kim, E. Shim, M. Lee, J. Org. Chem., 2004, 69, 4852-4855.

Hydroformylation of alkenes can be carried out in a few minutes under microwave activation at a relatively low pressure (2.7 atm) using commercially available catalysts and ligands. After 4 min of microwave irradiation, the corresponding aldehyde is formed in high yield.
E. Petricci, A. Mann, A. Schoenfelder, A. Rota, M. Taddei, Org. Lett., 2006, 8, 3725-3727.

The 6-DPPon/rhodium catalyst allows for the first time a room temperature/ambient pressure hydroformylation of various, structurally diverse terminal alkenes with low catalyst loadings. This protocol omits the need for special pressure equipment and should find wide application in organic synthesis.
W. Seiche, A. Schuschkowski, B. Breit, Adv. Syn. Catal., 2005, 1488-1494.

A regioselective intermolecular hydroacylation of vinalarenes, in which symmetric and mixed carboxylic anhydrides are used as acyl donors, is promoted by a cationic rhodium catalyst ligated by triphenylarsine.
Y.-T. Hong, A. Barchuk, M. J. Krische, Angew. Chem. Int. Ed., 2006, 45, 6885-6888.

Rhodium (I) bis-olefin complexes catalyzes the addition of electron-rich aromatic aldehydes to olefins to form ketones. Use of a more electron-deficient Rhodium catalyst results in faster reaction rates, better selectivity for linear ketone products and broader reaction scope.
A. H. Roy, C. P. Lenges, M. Brookhart, J. Am. Chem. Soc., 2007, 129, 2082-2093.

A cationic rhodium(I)/dppb complex catalyzed direct intermolecular hydroacylation of N,N-dialkylacrylamides with both aliphatic and aromatic aldehydes represents a versatile route to γ-ketoamides in view of high atom economy and commercial availability of substrates.
K. Tanaka, Y. Shibata, T. Suda, Y. Hagiwara, M. Hirano, Org. Lett., 2007, 9, 1215-1218.

Weinreb amides are efficiently converted into ketones by reaction with alkylidenetriphenylphosphoranes and in situ hydrolysis of the intermediate.
J. A. Murphy, A. G. J. Commeureuc, T. N. Snaddon, T. M. McGuire, T. A. Khan, K. Hisler, M. L. Dewis, R. Carling, Org. Lett., 2005, 7, 945-947.

While 3,4;5,6-di-O-isopropylidene-N-phthaloyl-D-glucosamine propane-1,3-diyl dithioacetal underwent fast β-elimination, the corresponding N-acetyl derivative was easily deprotonated with butyllithium to form the dilithiated intermediate. Stoichiometry and temperature were crucial factors for selective C-C coupling with various electrophiles.
Y.-L. Chen, R. Leguijt, H. Redlich, R. Fröhlich, Synthesis, 2006, 4212-4218.

1-Siloxy-1-alkenylcopper species were generated by 1,2-C^sp2-to-O silyl migration of the copper enolates of acyltriphenylsilanes. The alkenylcopper species reacted with methyl, benzyl, allylic, tributylstannyl halides and in the presence of Pd(0) catalyst with aryl and alkenyl iodides to give geometrically pure (Z)-enol silyl ethers.
A. Tsubouchi, K. Onishi, T. Takeda, J. Am. Chem. Soc., 2006, 128, 14268-14269.

The conversion of primary nitroalkanes into the corresponding α-nitro ketones readily proceeds using N-acylbenzotriazoles as acylation agents.
A. R. Katritzky, A. A. A. Abdel-Fattah, A. V. Gromova, R. Witek, P. J. Steel, J. Org. Chem., 2005, 70, 9211-9214.

Various oxo acid derivatives were obtained directly from the reaction of aliphatic and aromatic aldehydes with ω-alkenoic acid derivatives in the presence of rhodium(I) complexes and 2-amino-3-picoline.
E.-A. Jo, C.-H. Jun, Eur. J. Org. Chem., 2006, 2504-2507.

Catalytic amounts of weak bases such as sodium carbonate can carry out the ketonic decarboxylation of adipic acid into cyclopentanone selectively. This is in accordance with a mechanism involving decarboxylation and nucleophilic attack at a second carboxyl group. Stereogenic centres in the β-positions retain their stereochemistry.
M. Renz, A. Corma, Eur. J. Org. Chem., 2004, 2036-2039.

tert-Dodecanthiol-catalyzed generation of acyl radicals and their intramolecular addition to double bonds gave 2-substituted five- and six-membered cyclic ketones in good yields.
K. Yoshikai, T. Hayama, K. Nishimura, K.-I. Yamada, K. Tomioka, J. Org. Chem., 2005, 70, 681-683.

A highly enantio- and diastereoselective intramolecular Stetter reaction has been developed. Aliphatic and aromatic aldehydes and a broad range of trisubstituted Michael acceptors have been found to afford the desired products in good overall yield with high enantio- and diastereoselectivity.
J. Read de Alaniz, T. Rovis, J. Am. Chem. Soc., 2005, 127, 6284-6289.