Categories: C-C Bond Formation > Alcohols, Arenes >
Synthesis of benzylic alcohols
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Recent Literature
Suzuki-Miyaura cross-coupling of aryl halides and triflates with potassium
acetoxymethyltrifluoroborate afforded the corresponding benzylic alcohols in
good yields.
N. Murai, M. Yonaga, K. Tanaka, Org. Lett., 2012,
14, 1278-1281.
The combination of Me3SiO- and Bu4N+
serves as a general activator of organotrimethylsilanes for addition reactions.
A broad scope of bench-stable trimethylsilanes (including acetate, allyl,
propargyl, benzyl, dithiane, heteroaryl, and aryl derivatives) can be used as
carbanion equivalents for synthesis. Reactions are achieved at rt without the
requirement of specialized precautions that are commonplace for other
organometallics.
M. Das, D. F. O'Shea, J. Org. Chem., 2014,
79, 5595-5607.
The use of tri(tert-butyl)phosphine as ligand has a significant effect in
accelerating the Rh-catalyzed addition of aryl- and 1-alkenylboronic acids to aldehydes even
at room temperature.
M. Ueda, N. Miyaura, J. Org. Chem., 2000,
65, 4450-4452.
A Ni complex with a 1,5-diaza-3,7-diphosphacyclooctane ligand catalyzes a
reductive or redox-neutral coupling of aryl iodides with either aldehydes or
alcohols, respectively. The P2N2 ligand was found to avoid
deleterious aryl halide reduction pathways that dominate with more traditional
phosphines and NHCs.
E. S. Isbrandt, A. Nasim K. Zhao, S. G. Newman, J. Am. Chem. Soc.,
2021, 143, 14646-14656.
Tributylmagnesate (nBu3MgLi) and the more
reactive dibutylisopropylmagnesate (iPrnBu2MgLi)
induce facile iodine/bromine-magnesium exchange to provide various
polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using
this method proceeds with retention of configuration of the double bond.
A. Inoue, K. Kitagawa, H. Shinokubo, K. Oshima, J. Org. Chem., 2001,
66, 4333-4339.
Multicatalytic protocols convert alkenes, unsaturated aliphatic alcohols, and
aryl boronic acids into secondary benzylic alcohols with high
stereoselectivities under sequential catalysis that integrates alkene
cross-metathesis, isomerization, and nucleophilic addition.
A. Casnati, D. Lichosyt, B. Lainer, L. Veth, P. Dydio, Org. Lett., 2021, 23,
3502-3506.
A visible-light-induced cobalt-catalyzed asymmetric reductive 1,2-addition of
aryl iodides to aldehydes provides chiral benzyl alcohols in very good yield,
and high ee. This methodology offers mild reaction conditions, good
functionality tolerance, excellent enantiocontrol, the avoidance of mass metal
wastes, and the use of precious metal catalysts.
X. Jiang, H. Jiang, Q. Yang, Y. Cheng, L.-Q. Lu, J. A. Tunge, W.-J. Xiao, J. Am. Chem. Soc.,
2022, 144, 8347-8354.
Chiral amino thioacetate ligands were remarkably superior to the corresponding
amino alcohols as catalysts for enantioselective aryl transfer reactions. Low
catalyst loadings were sufficient to achieve excellent enantioselectivity as
well as high conversion in short reaction time.
M.-J. Jin, S. M. Sarkar, D.-H. Lee, H. Qiu, Org. Lett., 2008,
10, 1235-1237.
Diastereomeric aziridine carbinols are applied as efficient chiral ligand in a
catalyzed asymmetric arylation and sequential arylation-lactonization cascade.
The two diastereomers, which are facilely synthesized from the same chiral
source, function as pseudo enantiomers in arylation of aromatic aldehydes
providing the different enantiomers of the diarylmethanols with almost the same
excellent enantioselectivities.
X. Song, Y.-Z. Hua, J.-G. Shi, P.-P. Sun, M.-C. Wang, J. Chang, J. Org. Chem., 2014,
79, 6087-6093.
The value of stable and easily accessible triarylborane ammonia complexes as
precursors for arylzinc reagents in asymmetric catalysis is demonstrated.
Various chiral diarylmethanols were synthesized in high yield and
enantioselectivity.
S. Dahmen, M. Lormann, Org. Lett.,
2005,
7, 4597-4600.
A chiral N-heterocyclic carbene (NHC)-nickel complex catalyzes an
enantioconvergent upgrading reaction of simple racemic secondary alcohols to
enantioenriched tertiary alcohols. In this highly efficient formal asymmetric
alcohol α-C-H arylation, a dehydrogenation with phenyl triflate as a mild
oxidant is followed by asymmetric addition of arylboronic esters to the
transient ketones.
Y. Cai, S.-L. Shi, J. Am. Chem. Soc.,
2021, 143, 11963-11968.
A chiral zinc complex of salen is an efficient catalyst for the phenyl transfer
from an organozinc reagent to aromatic aldehydes and acetophenones with high
enantioselectivities.
K. Shimizu, H. Uetsu, T. Gotanda, K. Ito,
Synlett, 2015, 26, 1238-1242.
Enantiomerically enriched diarylmethanols have been prepared by catalyzed
asymmetric phenyl transfer reactions onto aromatic aldehydes with use of readily
available β-hydroxysulfoximines as catalysts. Various functionalized aldehydes
and heterocyclic substrates are tolerated, yielding synthetically relevant
products.
J. Sedelmeier, C. Bolm, J. Org. Chem., 2007,
72, 8859-8862.
Simple nickel complexes of bipyridine and PyBox catalyze the addition of aryl
halides to both aromatic and aliphatic aldehydes using zinc metal as the
reducing agent. This convenient approach tolerates acidic functional groups that
are not compatible with Grignard reactions, yet sterically hindered substrates
still couple in high yield.
K. J. Garcia, M. M. Gilbert, D. J. Weix, J. Am. Chem. Soc.,
2019,
141, 1823-1827.
The use of activated Magnesium (Rieke Magnesium) enables the preparation of
functionalized Grignard reagents at low temperatures. The Grignard reagents were
reacted with several electrophiles such as benzaldehyde, benzoyl chloride, or
allyl iodide. The reaction of benzoyl chloride yielded ketones with little or no
addition to the carbonyl functionality due to the low temperature.
J.-s. Lee, R. Valerde-Ortiz, A. Guijarro, R. D. Rieke, J. Org. Chem., 2000,
65, 5428-5430.
A variety of functionalized organozinc reagents undergo smooth addition
reactions at ambient temperature to carbonyl compounds and carbon dioxide in the
presence of stoichiometric amounts of MgCl2. Several reactions were
performed on a large scale.
S. Bernhardt, A. Metzger, P. Knochel, Synthesis, 2010, 3802-3810.
An efficient new methodology for the arylation of aldehydes is disclosed which
uses dirhodium(II) catalysts and N-heterocyclic carbene (NHC) ligands. An
N-heterocyclic carbene monocomplex of dirhodium(II) acetate was shown to
be the most active catalyst and was particularly efficient in the arylation of
alkyl aldehydes.
A. F. Trindade, P. M. P. Gois, L. F. Veiros, V. André, M. T. Duarte, C. A. M.
Afonso, S. Caddick, F. G. N. Cloke, J. Org. Chem., 2008,
73, 4076-4086.
The use of a thioether-imidazolinium chloride as a heterobidentate carbene
ligand precursor led to a high level of catalyst performance in the
palladium-catalyzed 1,2-addition of aryl-, heteroaryl-, and alkenylboronic acids
to aromatic, heteroaromatic, and aliphatic aldehydes.
M. Kuriyama, R. Shimazawa, R. Shirai, J. Org. Chem., 2008,
73, 1597-1600.
The 1,2-addition of aryl- or heteroarylboronic acids to aldehydes in the
presence of PdCl2 and P(1-Nap)3 affords carbinol
derivatives in very good yields. The reaction tolerates nitro, cyano, acetamido,
acetoxy, acetyl, carboxyl, trifluoromethyl, fluoro, and chloro groups and allows
the conversion of aliphatic aldehydes and hindered substrates.
C. Qin, H. Wu, J. Cheng, X. Chen, M. Liu, W. Zhang, W. Su, J. Ding, J. Org. Chem., 2007,
72, 4102-4107.
Anionic four-electron donor-based palladacycles were highly efficient,
practical catalysts for 1,4-additions of arylboronic acids with α,β-unsaturated
ketones and 1,2-additions of arylboronic acids with aldehydes and α-ketoesters.
P. He, Y. Lu, C.-G. Dong, Q.-S. Hu, Org. Lett., 2007,
9, 343-346.
Cationic Pd(II) complex-catalyzed addition of arylboronic acids to aldehydes
gave diarylmethanols in high yields with low catalyst loading. A one-pot
synthesis of unsymmetrical triarylmethanes from arylboronic acids, aryl
aldehydes, and electron-rich arenes was achieved in high yields.
S. Lin, X. Lu, J. Org. Chem., 2007,
72, 9757-9760.
The use of ZnCl2, Me3SiCH2MgCl, and LiCl
effectively minimizes problematic side reactions in the 1,2-addition of strongly
basic alkyl and aryl Grignard reagents to ketones. Aldimines give secondary
amines in high yield. The simplicity of this reliable ZnCl2•Me3SiCH2MgCl•LiCl
system might be attractive for industrial as well as academic applications.
M. Hatano, O. Ito, S. Suzuki, K. Ishihara, J. Org. Chem., 2010,
75, 5008-5016.
Aldehydes and siloxanes form methyl esters in a single step through mild
oxidative esterification in the presence of a palladium catalyst or,
alternatively, afford secondary alcohols via TBAF-promoted arylation in the
absence of a catalyst at increased temperatures.
R. Lerebours, C. Wolf, J. Am. Chem. Soc., 2006,
128, 13052-13053.
A H8-binol derived catalyst allows high enantioselectivity in the
reaction of diphenylzinc with both aliphatic and aromatic aldehydes. The use
of this catalyst avoids the need for additives such as diethylzinc and the
mild asymmetric reaction conditions make this chiral catalyst useful for
general synthesis.
Y.-C. Qin, L. Pu, Angew. Chem. Int. Ed., 2006,
45, 273-277.
In a highly efficient enantioselective organozinc addition to ketones, chiral
phosphoramide-Zn(II) complexes serve as conjugate Lewis acid-Lewis base
catalysts. From a variety of nonactivated aromatic and aliphatic ketones, the
corresponding optically active tertiary alcohols were obtained in high yields
with high enantioselectivities under mild reaction conditions.
M. Hatano, T. Miyamoto, K. Ishihara, Org. Lett., 2007,
9, 4535-4538.
The asymmetric addition of phenyl groups from diphenylzinc to ketones
gives good to excellent enantioselectivity with a range of substrates, using
a catalyst generated from a dihydroxy bis(sulfonamide) ligand and titanium
tetraisopropoxide.
C. Garcia, P. J. Walsh, Org. Lett., 2003,
5, 3641-3644.
An efficient palladium-catalyzed Suzuki-Miyaura reaction of oxygen
atom-substituted allylboronates with aryl/vinyl bromides, iodides, and triflates
provides various allylic siloxanes with high efficiency and excellent
regioselectivity. This alternative approach for the synthesis of allylic
alcohols offers broad substrate scope, excellent functional group tolerance, and
gram-scale preparation.
J. Li, X. Zhang, Y. Yao, Y. Gao, W. Yang, W. Zhao, J. Org. Chem., 2022, 87,
6951-6959.
A palladium(0) complex with chloroform is able to catalyze the addition of
arylboronic acids to aldehydes in the presence of a base, affording the
corresponding secondary alcohols in good yields. A catalytic amount of
chloroform seems to be essential for this reaction.
T. Yamamoto, T. Ohta, Y. Ito, Org. Lett.,
2005,
7, 4151-4155.
The addition of diverse organometallic reagents to
1-phenylsulfonylcyclopropanols enables a simple and high-yielding synthesis of
1-substituted cyclopropanols. The transformation is amenable to sp-, sp2-,
or sp3-hybridized organometallic C-nucleophiles under mild conditions,
and the use of enantioenriched substrates led to highly diastereoselective
additions.
R. M. Rivera, Y. Jang, C. M. Poteat, V. N. G. Lindsay,
Org. Lett., 2020, 22, 6510-6515.
Kinetic vs thermodynamic deprotonation studies on secondary and tertiary
sulfonamides using n-BuLi have been carried out. Application of the
developed conditions allows the synthesis of diverse sulfonamide products
(E=CH(OH)Ph).
S. L. MacNeil, O. B. Familoni, V. Snieckus, J. Org. Chem, 2001,
66, 3662-3670.
Various N-acylethylenediamine-based ligands were screened as
catalysts for the asymmetric addition of vinylzinc reagents to aldehydes.
The optimized ligand was found to catalyze the formation of (E)-allylic
alcohols with high enantioselectivities for both aromatic and α-branched
aldehydes, and vinylzinc reagents derived from both bulky and straight chain
terminal alkynes.
C. M. Sprout, M. L. Richmond, C. T. Seto, J. Org. Chem., 2005,
70, 7408-7417.
A combination of weak Lewis acid (LiCl) and weak Brønsted acid (hexafluoroisopropanol,
HFIP) promotes efficiently the Friedel-Crafts reaction of electron-rich aromatic
compounds with ethyl glyoxylate.
M. Willot, J. Chen, J. Zhu, Synlett, 2009,
577-580.
The asymmetric Friedel-Crafts reaction of N,N-dialkylanilines with
ethyl glyoxylate has been achieved by the catalysis of titanium complexes of
BINOL derivatives to give the corresponding mandelic acid ethyl esters in
high yields (85-99%) and good to excellent enantioselectivity (80-96.6% ee).
Y. Yuan, X. Wang, X. Li, K. Ding, J. Org. Chem.,
2004, 69, 146-149.
Enantioconvergent arylation reactions of boronic acids and racemic β-stereogenic
α-keto esters are catalyzed by a chiral (diene)Rh(I) complex and provide a wide
array of β-stereogenic tertiary aryl glycolate derivatives with high levels of
diastereo- and enantioselectivity.
S. L. Bartlett, K. M. Keiter, J. S. Johnson, J. Am. Chem. Soc., 2017,
139, 3911-3916.
Chiral allenes appended with basic functionality can serve as ligands for
transition metals. An allene-containing bisphosphine coordinated to Rh(I)
promotes the asymmetric addition of arylboronic acids to α-keto esters with high
enantioselectivity. Solution and solid-state structural analysis reveals that
one olefin of the allene can coordinate to transition metals, generating bi- and
tridentate ligands.
F. Cai, X. Pu, X. Qi, V. Lynch, A. Radha, J. M. Ready, J. Am. Chem. Soc., 2011,
133, 18066-18069.
