Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Synthesis of β-hydroxy ketones and aldehydes
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Recent Literature
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.
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.
A proazaphosphatrane is a very efficient catalyst for Mukaiyama aldol reactions
of aldehydes with trimethylsilyl enolates in THF solvent. The reaction
conditions are mild and operationally simple, and a variety of aryl functional
groups, such as nitro, amino, ester, chloro, trifluorometh yl, bromo, iodo,
cyano, and fluoro groups, are tolerated.
V. R. Chintareddy, K. Wadhwa, J. G. Verkade, J. Org. Chem., 2009,
74, 8118-8132.
An indium triiodide catalyst promoted the Mukaiyama Aldol Reaction of silyl
enolates with esters to form β-hydroxycarbonyl compounds in the presence of
hydrosilanes. Various esters were applicable, and the high chemoselectivity of
this system brings compatibility to many functional groups, such as alkenyl,
alkynyl, chloro, and hydroxy.
Y. Inamoto, Y. Nishimoto, M. Yasuda, A. Baba, Org. Lett., 2012,
14, 1168-1171.
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.
An efficient copper-catalyzed aldol reaction of readily available vinyl azides with
trifluoromethyl ketones provides trifluoromethylated compounds under mild conditions in
very good
yield.
Z. Liu, Z. Zhang, G. Zhu, Y. Zhou, L. Yang, W. Gao, L. Tong, B. Tang,
Org. Lett., 2019, 21, 7324-7328.
Treatment of vinyl ketones with a combination of TiCl4 and n-Bu4NI
followed by an addition of a variety of aldehydes provides syn-α-iodomethyl-β-hydroxy
ketones with high stereoselectivity. The use of n-Bu4NBr or
n-Bu4NCl provides the corresponding bromo or chloro compounds in
good yields.
Z. Han, S. Uehira, H. Shinokubo, K. Oshima, J. Org. Chem., 2001,
66, 7854-7857.
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.
The addition of bromomagnesium 2-vinyloxy ethoxide to various aldehydes in the
presence of 10 mol% Sc(OTf)3 provides a broad range of functionalized
protected aldol compounds. A Swern oxidation-CBS reduction sequence enables the
preparation of chiral protected aldol products.
P. Quinio, L. Kohout, D. S. Roman, J. Gaar, K. Karahiosoff, P. Knochel,
Synlett, 2016, 27, 1715-1719.
Catalytic enone hydrometallation represents a promising strategy for enolate
generation, circumventing the utilization of preformed enol or enolate
derivatives. Metal-catalyzed reductive condensation of α,β-unsaturated carbonyl compounds with aldehydes in the presence of a hydride donor enables highly
diastereoselective aldol and Michael cycloreductions.
T.-G. Baik, A. L. Luis, L.-C. Wang, M. J. Krische, J. Am. Chem. Soc., 2001,
123, 5112-5113.
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.
Related
A gold-catalyzed hydroamination of propargylic
alcohols with anilines provides 3-hydroxyimines. A subsequent reduction gives
1,3-amino alcohols with high syn selectivity. By using a
catalytic amount of aniline, 3-hydroxyketones can be obtained in high yield
directly from propargylic alcohols. And a selective formation of 3-aminoketones via a rearrangement/hydroamination
pathway is also described.
V. Laserna, M. J. Porter, T. D. Sheppard, J. Org. Chem., 2019,
84, 11391-11406.