Categories: C-C Bond Formation > Oxygen-containing molecules > Alcohols >
Synthesis of alcohols
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Recent Literature
β-Alkylation of various secondary alcohols with primary alcohols has been
achieved in the presence of [Cp*IrCl2]2 (Cp* =
pentamethylcyclopentadienyl) catalyst and a base. This reaction proceeds in
good to excellent yield via successive hydrogen-transfer reactions and aldol
condensation.
K.-I. Fujita, C. Asai, T. Yamaguchi, F. Hanasaka, R. Yamaguchi, Org.
Lett., 2005,
7, 4017-4019.
A cobalt-catalyzed reductive hydroformylation of terminal and
1,1-disubstituted alkenes in the presence of CO and H2 provides
one-carbon homologated alcohols. For minimally functionalized alkenes,
anti-Markovnikov products with exclusive linear regiocontrol are obtained.
C. S. MacNeil, L. N. Mendelsohn, T. P. Pabst, G. Hierlmeier, P. J. Chirik, J. Am. Chem. Soc.,
2022, 144, 19219-19224.
A neighboring boronate group in vicinal bis(boronic esters) provides a
dramatic rate acceleration in transmetalation to copper and thereby enables
unprecedented site-selective cross-couplings allyl, alkynyl, and propargyl
electrophiles as well as a simple proton. This cross-coupling operates under
practical experimental conditions.
N. Xu, Z. Kong, J. Z. Wang, G. J. Lovinger, J. P. Morken, J. Am. Chem. Soc.,
2022, 144, 17815-17823.
A neighboring boronate group in vicinal bis(boronic esters) provides a
dramatic rate acceleration in transmetalation to copper and thereby enables
unprecedented site-selective cross-couplings allyl, alkynyl, and propargyl
electrophiles as well as a simple proton. This cross-coupling operates under
practical experimental conditions.
N. Xu, Z. Kong, J. Z. Wang, G. J. Lovinger, J. P. Morken, J. Am. Chem. Soc.,
2022, 144, 17815-17823.
An asymmetric α-alkylative reduction of prochiral ketones with primary
alcohols has been disclosed. The reaction is catalyzed by both iridium and
ruthenium complexes and gave optically active alcohols with elongation of
the carbon skeleton with high enantioselectivity.
G. Onodera, Y. Nishibayashi, S. Uemura, Angew. Chem. Int. Ed.,
2006,
45, 3819-3822.
A ruthenium-catalyzed transfer hydrogenation/carbon-carbon bond formation
between an array of ketones and primary alcohols serves as an alternative
synthetic route for secondary alcohols.
C. S. Cho, B. T. Kim, T.-J. Kim, S. C. Shim, J. Org. Chem., 2001,
66, 9020-9022.
Very low loadings of iridium(I) complexes having an imidazol-2-ylidene ligand
with benzylic wingtips efficiently catalyze the β-alkylation of secondary
alcohols with primary alcohols and acceptorless dehydrogenative formation of
quinolines from 2-aminobenzyl alcohol and ketones through a borrowing hydrogen
pathway to provide the desired products in good yields.
S. Genç, B. Arslan, S. Gülcemal, S. Günnaz, B. Çetinkaya, D. Gülcemal, J. Org. Chem., 2019, 84,
6286-6297.
RuCl2(PPh3)3 as a precatalyst enables a simple
cross dehydrogenative coupling between two different primary alcohols via a
borrowing-hydrogen approach. The present methodology is applicable to a large
variety of alcohols including long chain aliphatic alcohols and heteroaryl
alcohols.
S. Manojveer, S. Salahi, O. F. Wendt, M. T. Johnson, J. Org. Chem., 2018, 83,
10864-10870.
A simple method for the chemo- and regioselective, direct catalytic allylic
alkylation of aldehydes and cyclic ketones has been developed. The
combination of palladium and enamine catalysis furnished α-allylic alkylated
aldehydes and cyclic ketones in high yields.
I. Ibrahem, A. Córdova, Angew. Chem. Int. Ed., 2006,
45, 1952-1956.
A bipyridine-ligated nickel mediates the addition of functionalized aryl halides,
a vinyl halide, and a vinyl triflate to epoxides under reducing conditions. For
terminal epoxides, the regioselectivity of the reaction depends upon the
cocatalyst employed. Iodide cocatalysis results in opening at the less hindered
position via an iodohydrin intermediate. Titanocene cocatalysis results in
opening at the more hindered position.
Y. Zhao, D. J. Weix, J. Am. Chem. Soc., 2014,
136, 48-51.
An enantioselective α-arylation of aldehydes has been accomplished using
diaryliodonium salts and a combination of copper and organic catalysts. These
mild catalytic conditions allow the enantioselective construction and retention
of enolizable α-formyl benzylic stereocenters, a valuable synthon for the
production of medicinal agents.
A. E. Allen, D. W. C. MacMillan, J. Am. Chem. Soc., 2011,
133, 4260-4263.
A one-pot alkylation-silylation reaction of various epoxides with R3Al-R'3SiOTf
occurs stereospecifically to give the corresponding alkylation-silylation
products in excellent yields.
P. Shanmugam, M. Miyashita, Org. Lett., 2003, 3265-3268.
In a rhenium-catalyzed oxyalkylation of alkenes, hypervalent iodine(III)
reagents derived from widely occurring aliphatic carboxylic acids were not only
an oxygenation source but also an alkylation source via decarboxylation. The
reaction offers a wide substrate scope, totally regiospecific
difunctionalization, mild reaction conditions, and ready availability of both
substrates.
Y. Wang, L. Zhang, Y. Yang, P. Zhang, Z. Du, C. Wang, J. Am. Chem. Soc., 2013,
135, 18048-18051.
The reaction of dianions, derived from the reductive opening of phthalan
(n=1) or isochroman (n=2) with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl
(DTBB) at 0°C, with several epoxides gave 1,6- and 1,7-diols, respectively.
M. Yus, T. Soler, F. Foubelo, Tetrahedron, 2002, 58,
7009-7016.