Categories: C-O Bond Formation > Synthesis of alcohols (hydroxylation) >
Synthesis of β-hydroxy ketones, esters, nitriles and related compounds
| Related:
|
 |
 |
Recent Literature
The direct addition of water and a variety of alcohols to activated olefins
was observed in the presence of nucleophilic phosphine catalysts. Unlike
existing methods, the reactions proceed at room temperature and in the absence
of transition metals, or strong acids or bases.
I. C. Stewart, R. G. Bergman, F. D. Toste, J. Am. Chem. Soc., 2003,
125, 8696-8697.
A combined amino- and N-heterocyclic carbene (NHC)-catalyzed one-pot
reaction sequence using commercially available catalysts at low catalyst
loadings gives β-hydroxy and β-amino esters in high yield and excellent
enantiopurity. The generation of quaternary stereocenters and application in
gram-scale synthesis were also realized, with no requirements of inert or
anhydrous reaction conditions.
H. Jiang, B. Gschwend, Ł. Albrecht, K. A. Jørgensen, Org. Lett., 2010,
12, 5052-5055.
Bidentate Oxazoline-substituted imidazolium salts based on [2.2]paracyclophane
with planar and central chirality can be used as ligand in Cu(I)-catalyzed
asymmetric β-boration of α,β-unsaturated esters, giving the desired products in
high enantioselectivities and yields.
Z. Niu, J. Chen, Z. Chen, M. Ma, C. Song, Y. Ma, J. Org. Chem.,
2015,
80, 602-608.
A Rh-catalyzed hydroboration of α, β-unsaturated carbonyl compounds with
pinacolborane proceeds with high levels of regio-, diastereo-, and
enantioselectivities to provide products with two vicinal stereocenters. Through
the appropriate choice of substrate geometry (E or Z) and ligand
enantiomer, all possible diastereoisomers are readily accessible.
T.-T. Gao, W.-W. Zhang, X. Sun, H.-X. Lu, B.-J. Li, J. Am. Chem. Soc.,
2019,
141, 4670-4677.
An N-heterocyclic carbene-catalyzed oxidative single-electron-transfer reaction
enables the β-hydroxylation of enals through a pathway involving multiple
radical intermediates, as supported by experimental observations. The reaction
allows a highly enantioselective access to β-hydroxyl esters that are widely
found in natural products and bioactive molecules.
Y. Zhang, Y. Du, Z. Huang, J. Xu, X. Wu, Y. Wang, M. Wang, S. Yang, R. D.
Webster, Y. R. Chi, J. Am. Chem. Soc., 2015,
137, 2416-2419.
An efficient intermolecular conjugate addition of various primary and secondary
alcohols to unsaturated ketones and esters is catalyzed by the free carbene
derived from IMes·HCl. No oligomerization is observed under these mild
conditions. In addition to reactions with activated alkenes, IMes catalyzes the
formation of vinyl ethers through the 1,4-addition of alcohols to ynones.
E. M. Phillips, M. Riedrich, K. A. Scheidt, J. Am. Chem. Soc., 2010,
132, 13179-13181.
A variety of α,β-unsaturated ketones effectively reacted in an efficient chromium(III) chloride-catalyzed Michael-type
addition with either water or
alcohols to give the corresponding β-hydroxyl ketones or β-alkoxyl ketones in
good yields with excellent functional group compatibility.
The approach was further utilized for the preparation of synthetically useful tetrahydrofuran
derivatives.
J.-J. Yun, X.-Y. Liu, W. Deng, X.-Q. Chu, Z.-L. Shen, T.-P. Loh, J. Org. Chem., 2018, 83,
10898-10907.
A new palladium-catalyzed method allows the oxygenation of unactivated sp3
C-H bonds of a wide variety of alkane substrates containing readily
available oxime and/or pyridine directing groups with extremely high levels
of chemo-, regio-, and in some cases diastereoselectivity.
L. V. Desai, K. L . Hull, M. S. Sanford, J. Am. Chem. Soc.,
2004,
126, 9542-9543.
R. Shintani, K. Okamoto, T. Hayashi, Org. Lett.,
2005,
7, 4757-4759.
Related
Low-valent Cp2TiCl selectively reduces selected α,β-epoxy ketones
to the corresponding aldol products under mild conditions. A chiral epoxide was
converted without any loss of optical purity. The addition of collidine
hydrochloride enables a system catalytic in titanocene.
C. Hardouin, F. Chevallier, B. Rousseau, E. Doris, J. Org. Chem., 2001,
66, 1046-1048.
