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Synthesis of β-hydroxy ketones and aldehydes

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Rhodium-catalyzed catalytic hydrogenation of methyl vinyl ketone (MVK) and ethyl vinyl ketone (EVK) in the presence of various aldehydes at ambient temperature and pressure using tri-2-furylphosphine as ligand enables formation of aldol products with high levels of syn-diastereoselectivity. Hydrogen-labile functional groups, including alkynes, alkenes, benzylic ethers, and nitroarenes, remain intact under the coupling conditions.
C.-K. Jung, S. A. Garner, M. J. Krische, Org. Lett., 2006, 8, 519-522.

A tandem 1,4-reduction-aldol cyclization is induced by exposure of monoenone monoketones to catecholborane in THF at ambient temperature. Six-membered cyclic aldol products are formed in excellent yield with high levels of syn diastereoselectivity for aromatic and heteroaromatic enones. Five-membered ring formation proceeds less readily, but the yield is improved through addition of Rh(I) salts.
R. R. Huddleston, D. F. Cauble, M. J. Krische, J. Org. Chem., 2003, 68, 11-14.

The reaction of α-bromoaldehydes with aldehydes in the presence of GeCl₂-dioxane gave cross-aldol equivalents with syn-selectivity. The initially formed β-germoxyaldehydes did not lead to side products. Addition of a catalytic amount of Bu₄NBr improved the yield and selectivity.
M. Yusada, S.-Y. Tanaka, A. Baba, Org. Lett., 2005, 7, 1845-1848.

Mild and selective heterobimetallic-catalyzed decarboxylative aldol reactions of allyl β-keto esters with aldehydes are promoted by Pd(0)- and Yb(III)-DIOP complexes at room temperature. The optimized reaction conditions require the addition of both metals.
S. Lou, J. A. Westbrook, S. E. Schaus, J. Am. Chem. Soc., 2004, 126, 11440-11441.

An Et₃SiH-promoted diastereoselective reductive aldol reaction has been developed using InBr₃ as a catalyst. This three-component reaction afforded only silyl aldolates as products without any side reactions.
I. Shibata, H. Kato, T. Ishida, M. Yasuda, A. Baba, Angew. Chem. Int. Ed., 2004, 43, 711-714.

The Rh-catalyzed reaction of 9-aryl-9-borabicyclo[3.3.1]nonanes with α,β-unsaturated ketones and aldehydes gave high yields of tandem 1,4-addition-aldol reaction products with high syn selectivity. The mechanism is discussed.
K. Yoshida, M. Ogasawara, T. Hayashi, J. Am. Chem. Soc., 2002, 124, 10984-10985.

Hydroxymethylation of dimethylsilyl (DMS) enolates using aqueous formaldehyde solution is catalyzed by scandium(III) fluoride in aqueous media to give the corresponding β-hydroxy ketones in good to excellent yields, but TMS enolates react sluggishly under the same conditions. ScF₃ has been shown to be a unique catalyst for this reaction.
M. Kokubo, S. Kobayashi, Synlett, 2008, 1562-1564.

The synthesis of new C₁-symmetric benzene-bridged aminosulfoximines is described. These aminosulfoximines are capable of serving as efficient ligands in copper-catalyzed enantioselective Mukaiyama-type aldol reactions.
M. Langner, C. Bolm, Angew. Chem. Int. Ed., 2004, 43, 5984-5987.

A new, diastereoselective three-component halo aldol reaction has been discovered for the tandem formations of I-C/C-C bonds, which gives aldol adducts in good yields. The key intermediates (allenolates and 1-iodo-3-siloxy-1,3-butadienes), were directly monitored by ¹H NMR.
H.-X. Wei, S. H. Kim, G. Li, Org. Lett., 2002, 4, 3691-3693.

Related

A linchpin coupling protocol is based on anion relay chemistry (ARC). The addition of an anion to an epoxide, bearing on a distal carbon a trialkyl silyl group and an anion stabilizing group furnishes upon epoxide ring opening an oxyanion. Addition of HMPA triggers a solvent controlled 1,4-Brook rearrangement leading to a new distal anion, which reacts with various electrophiles.
A. B. Smtih, III, M. Xiang, J. Am. Chem. Soc., 2006, 128, 66-67.