Categories: C-C Bond Formation > Oxygen-containing molecules > Alcohols >
Synthesis of alcohols
| Related: |
 |
 |
 |
 |
|||
 |
 |
 |
 |
Name Reactions
Recent Literature
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.
The nucleophilicity of magnesium ate complexes derived from Grignard
reagents and alkyllithiums is remarkably increased compared to that of the
original RLi or RMgX, while the basicity of R3MgLi is decreased,
which allows a highly efficient alkyl-selective addition to ketones.
M. Hatano, T. Matsumura, K. Ishihara, Org. Lett., 2005,
7, 573-576.
A highly efficient Zn-catalyzed alkylation of ketones and aldimines with
Grignard reagents via trialkylzinc(II) ate complexes minimizes
problems with the use of only Grignard reagents, which leads to reduction
and aldol side products, and the yield of desired alkylation products could
be improved.
M. Hatano, S. Suzuki, K. Ishihara, J. Am. Chem. Soc., 2006,
128, 9998-9999.
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.
LnCl3•2 LiCl (Ln = La, Ce, Nd) are superior promoter
for the addition of various organometallic reagents to ketones. They also
catalyze efficiently the addition of organomagnesium compounds to imines.
A. Krasovskiy, F. Kopp, P. Knochel, Angew. Chem. Int. Ed., 2006,
45, 497-500.
NdI2 is viable one-electron reducing agent in coupling
reactions between alkyl chlorides and carbonyl compounds.
W. J. Evans, P. S. Workman, N. T. Allen, Org. Lett., 2003,
5, 2041-2042.
Barbier-type alkylation of esters with alkyl iodides proceeded smoothly at
room temperature in the presence of metallic strontium under argon to afford
the corresponding dialkylated alcohols in good yields.
N. Miyoshi, T. Matsuo, M. Wada, Eur. J. Org. Chem., 2005,
4253-4255.
A refined version of Charette's procedure for the preparation of zinc reagents
from Grignard reagents minimizes the side reactions in the subsequent catalytic,
enantioselective n-alkyl addition of commercially unavailable di(n-alkyl)zinc
reagents to aldehydes and ketones.
M. Hatano, T. Mizuno, K. Ishihara, Synlett, 2010,
2024-2028.
A highly enantioselective addition of dialkylzincs to aromatic, aliphatic,
and heteroaromatic aldehydes is based on conjugate Lewis acid-Lewis base
catalysis using bifunctional BINOL ligands.
M. Hatano, T. Miyamoto, K. Ishihara, J. Org. Chem., 2006,
71, 6474-6484.
The catalytic asymmetric addition of alkyl groups to ketones under highly
concentrated and solvent-free conditions permits reduction in catalyst
loading by a factor of 2- to 40-fold compared with standard reaction
conditions employing toluene and hexanes. Using cyclic conjugated enones,
solvent-free asymmetric addition followed by a diastereoselective
epoxidation using 5.5 M decane solution of tert-butyl hydroperoxide
generated epoxy alcohols.
S.-J. Jeon, H. Li, P. J. Walsh, J. Am. Chem. Soc.,
2005,
127, 16416-16425.
S.-J. Jeon, P. J. Walsh, J. Am. Chem. Soc., 2003,
125, 9544-9545.
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.
Addition of diethylzinc to aromatic, aliphatic, and α,β-unsaturated aldehydes
afforded secondary alcohols in high yield and enantiomeric excess in the
presence of β-pinene derived amino alcohols 2-MAP and 3-MAP as chiral
auxiliaries. These two amino alcohols provide antipodal enantiofacial
selectivity in the dialkylzinc addition reaction.
C. M. Binder, A. Bautista, M. Zaidlewicz, M. P. Krzemiski, A. Oliver, B.
Singaram, J. Org. Chem., 2009,
74, 2337-2343.
Highly reactive RMgBr reagents were effectively deactivated by bis[2-(N,N-dimethylamino)ethyl]
ether. These chelated Grignard reagents were employed in a highly
enantioselective addition to aldehydes catalyzed by a complex of commercially
available (S)-BINOL and Ti(Oi-Pr)4 under mild
conditions.
C.-S. Da, J.-R. Wang, X.-G. Yin, X.-Y. Fan, Y. Liu, S.-L. Yu, Org. Lett., 2009,
11, 5578-5581.
Simple procedure, room temperature, and low catalyst loading are the
characteristics of a new ClCr(Salen)-catalyzed enantioselective 1,2-addition
of the rather unreactive Me2Zn to a broad range of aldehydes.
P. G. Cozzi, P. Kotrusz, J. Am. Chem. Soc.,
2006,
128, 4940-4941.
Chiral α-(carbamoyloxy)alkylcopper reagents, prepared using Hoppe's sBuLi/(-)-sparteine
methodology and subsequent transmetalations with ZnCl2 and CuCN,
reacted with various electrophiles to give enantiomerically pure alcohols after
deprotection.
J. P. N. Papillon, R. J. K. Taylor, Org. Lett., 2002, 4,
119-122.
Three highly enantio- and diastereoselective one-pot procedures for the
synthesis of cyclopropyl and iodocyclopropyl alcohols with up to four
contiguous stereocenters are reported. Route 1 and 2 involve asymmetric
addition of an alkylzinc reagent to an enal followed by diastereoselective
cyclopropanation using either diiodomethane or iodoform to generate the zinc
carbenoid, leading to cyclopropyl or iodocyclopropyl alcohols, respectively.
Route 3 entails asymmetric vinylation of an aldehyde with divinylzinc
reagents and subsequent diastereoselective cyclopropanation.
H. Y. Kim, A. E. Lurain, P. Garcia-Carcia, P. J. Carroll, P. J. Walsh, J.
Am. Chem. Soc.,
2005,
127, 13138-13139.
A new fluorous ligand showed excellent asymmetric induction on the addition
of dimethylzinc to aldehydes. This ligand can be conveniently recycled and will
be useful for synthesis of bioactive compounds with a methyl carbinol moiety.
Y. S. Sokeirik, H. Mori, M. Omote, K. Sato, A. Tarui, I. Kumadaki, A. Ando, Org. Lett., 2007,
9, 1927-1929.
(1S,2R)-2-(N-Morpholino)-1,2-dicyclohexylethanol promotes
the enantioselective addition of diethylzinc to aldehydes in high enantiomeric
excess.
W. A. Nugent, Org. Lett., 2002, 4, 2133-2136.
An enantioselective 1,2- and 1,4-addition of organozinc compounds to
aldehydes and cyclic enones using bis(oxazolines) as chiral ligands is
reported. Ligands with hydroxymethylene side chains gave the best results
and it is suggested that during copper-catalyzed 1,4-addition to enones the
occurrence of a bimetallic catalyst is decisive for high enantiocontrol in
these additions.
M. Schinnerl, M. Seitz, A. Kaiser, O. Reiser, Org. Lett., 2001,
3, 4259-4262.
Fluorous chiral BINOLs were prepared and used as the ligands for the
titanium catalyzed asymmetric addition of Et2Zn to aromatic
aldehydes. Products were isolated by simple fluorous-organic biphase and
fluorous solid phase extraction techniques with similar enantioselectivities
to that attained in the non-fluorous system. The recovered FBINOLs can be
recycled.
Y. Nakamura, S. Takeuchi, K. Okumura, Y. Ohgo, D. P. Curran, Tetrahedron,
2002, 58, 3963-3969.
A wide range of α-prenylated alcohol derivatives could be obtained in good
yields by highly α-regioselective zinc-mediated prenylation of various aldehydes
and ketones with prenyl bromide at 120°C in HMPA. By simply altering the
reaciton solvent and temperature, the method allows the achievement of a highly
notable opposite regiocontrol, providing the expected regiochemical product.
L.-M. Zhao, H.-S. Jin, L.-J. Wan, L.-M. Zhang, J. Org. Chem., 2011,
76, 1831-1837.
A low loading of a proazaphosphatrane compound efficiently catalyzes the reaction of trimethylsilylacetonitrile
(TMSAN) with
aldehydes for the synthesis of
β-hydroxynitriles under mild reaction conditions. Various functional groups were tolerated, and good to excellent yields were obtained.
K. Wadhwa, J. G. Verkade, J. Org. Chem., 2009,
74, 5683-5686.
α-Halonitriles react with alkyllithium, organomagnesium, and lithium
dimethylcuprate reagents generating reactive, metalated nitriles. The rapid
halogen-metal exchange with alkyllithium and Grignard reagents allows
Barbier-type reactions with various electrophiles.
F. F. Fleming, Z. Zhang, W. Liu, P. Knochel, J. Org. Chem., 2005,
70, 2200-2005.
Alkoxide-induced nucleophilic pentafluoroethylation and trifluoromethylation
of aldehydes, ketones, and imines using pentafluoroethyl phenyl sulfone and
trifluoromethyl phenyl sulfone, respectively, have been successfully achieved.
G. K. S. Prakash, Y. Wang, R. Mogi, J. Hu, T. Mathew, G. A. Olah, Org. Lett., 2010,
12, 2932-2935.
