Categories: C-Cl Bond Formation >
Synthesis of chlorohydrins
Recent Literature
Highly regioselective ring opening of epoxides to halohydrins has been
carried out in impressive yields with hydrogen and lithium halides in presence
of β-cyclodextrin using water as solvent.
M. Arjun Reddy, K. Surendra, N. Bhanumathi, K. Rama Rao, Tetrahedron,
2002, 58, 6003-6008.
The use of trihaloisocyanuric acid/triphenylphosphine enables a regioselective
conversion of epoxides to vicinal chloro-/bromohydrins and vicinal dihalides
under mild and neutral conditions in acetonitrile. The reactions proceed
smoothly in high yield at room temperature and at reflux, respectively, over a
short time.
V. S. C. de Andrade, M. C. S. de Mattos,
Synthesis, 2016, 48, 1381-1388.
The preparation of diverse β-chloroethers, β-chloroacetates, and
chlorohydrins is efficiently achieved under mild conditions by reaction of
alkenes with trichloroisocyanuric acid in alcohols, acetic acid or aqueous
acetone, respectively.
G. Fonseca Mendonça, A. Manzolillo Sanseverino, M. C. S. de Mattos, Synthesis,
2003, 45-48.
G. Fonseca Mendonça, A. Manzolillo Sanseverino, M. C. S. de Mattos, Synthesis,
2003, 45-48.
A green, oxidant-free electrochemical method enables radical bromination,
chlorination and trifluoromethylation-formyloxylation of various alkenes with
readily available halogen radical (NaCl, NaBr), and trifluoromethyl radical (CF3SO2Na)
sources in DMF as formyloxylation reagent in an undivided electrochemical cell.
X. Sun, H.-X. Ma, T.-S. Mei, P. Fang, Y. Hu,
Org. Lett., 2019, 21, 3167-3171.
SnCl4 and TiCl4 as Lewis acids and chloride
nucleophiles enable selective and regiodivergent openings of unsymmetrical
phenonium ions at either the substituted internal position (SnCl4) or
unsubstituted terminal position (TiCl4). These reactions are highly
selective, stereospecific, operationally simple, and proceed in good to
excellent yields.
S. Xu, H. M. Holst, S. B. McGuire, N. J. Race, J. Am. Chem. Soc.,
2020, 142, 8090-8096.
The use of the commercially available trichloromethanesulfonyl chloride enables
an efficient α-chlorination of aldehydes, including a catalytic asymmetric
version, under very mild reaction conditions. This chlorinating reagent
facilitates workup and purification of the product, and minimizes the formation
of toxic, chlorinated organic waste.
C. Jimeno, L. Cao, P. Renaud, J. Org. Chem.,
2016,
81, 1251-1255.
PhICl2 in wet DMF forms an efficient system for difunctionalization
of various alkenes to provide either regioselective chloroformyloxylated
products or α-chlorinated olefinic products, depending on the type of structure
of the original unsaturated starting material. The mechanism of the reaction is
proposed and discussed.
L. Liu, D. Zhang-Negrerie, Y. Du, K. Zhao, Org. Lett., 2014,
16, 436-439.
An optically active, C2-symmetric allene-containing bisphosphine oxide catalyzes
the addition of SiCl4 to meso-epoxides with high
enantioselectivity. The epoxide opening likely involves generation of a Lewis
acidic, cationic (bisphosphine oxide)SiCl3 complex.
X. Pu, X. Qi, J. M. Ready, J. Am. Chem. Soc., 2009,
131, 10364-10365.
Related
The reaction of (chloromethyl)magnesium chloride-lithium chloride (ClCH2MgCl·LiCl),
a mixed lithium-magnesium carbenoid, with aromatic aldehydes bearing various
functional groups enables a highly chemoselective synthesis of a range of
aromatic chlorohydrins in high yields.
R. H. V. Nishimura, V. E. Murie, R. A. Soldi, G. C. Clososki, Synthesis, 2015, 47,
1455-1460.
The generation of highly unstable chloromethylmagnesium chloride in a
continuous flow reactor and a subsequent reaction with aldehydes and ketones
provides chlorohydrins and epoxides in good yields within a total residence time
of only 2.6 s. The outcome of the reaction can be tuned by simply using either a
basic or an acidic quench.
T. von Keutz, D. Cantillo, C. O. Kappe,
Org. Lett., 2020, 22, 7537-7541.