Categories: C-C Bond Formation > Oxygen-containing molecules > Alcohols >
Synthesis of homoallylic alcohols
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AgF and (R)-DIFLUORPHOS predominantly formed a 1:1 complex that
provided high enantioselectivity for the asymmetric Sakurai-Hosomi
allylation of various simple ketones. Only 1,2-adducts were obtained from
both acyclic and cyclic conjugate ketones. Highly diastereo- and
enantioselective reactions with E- or Z-crotyltrimethoxysilane
and racemic allylsilanes are described.
M. Wadamoto, H. Yamamoto, J. Am. Chem. Soc.,
2005,
127, 14556-14557.
A general and mild CuCl-TBAT-catalyzed allylation of aldehydes, ketones, and
imines was developed using allyltrimethoxysilane as the allylating reagent.
Mechanism studies indicated that the copper alkoxide,
allylfluorodimethoxysilane, and allyltrimethoxysilane are essential to
promote the reaction efficiently.
S. Yamasaki, K. Fujii, R. Wada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc.,
2002,
124, 6536-6537.
In acetonitrile as solvent and in the presence of a simple cobalt halide as
catalyst, the reduction by zinc dust of a mixture of aldehydes or ketones
and allylic acetates affords the corresponding homoallylic alcohols in good
yields.
P. Gomes, C. Gosmini, J. Périchon, Synthesis,
2003, 1909-1915.
A rapid and efficient procedure for the solvent-free synthesis of
homoallylic and homopropargyl alcohols has been achieved by zinc-mediated
Barbier-type reaction of carbonyl compounds at room temperature.
J.-X. Wang, X. Jia, T. Meng, L. Xin,
Synthesis, 2005, 2669-2672.
J.-X. Wang, X. Jia, T. Meng, L. Xin,
Synthesis, 2005, 2669-2672.
A range of polysubstituted allylic zinc chlorides were obtained in good yield
using a LiCl-mediated zinc dust insertion in polysubstituted allylic chlorides.
A highly diastereoselective synthesis of homoallylic alcohols bearing up to two
adjacent quaternary centers by the addition of polysubstituted allylic zinc
reagents to carbonyl compounds.
H. Ren, G. Dunet, P. Mayer, P. Knochel, J. Am. Chem. Soc., 2007,
129, 5376-5377.
Trapping of β,γ-alkynyl aldehydes, generated in situ by treatment of alkynyloxiranes with a
catalytic amount of Sc(OTf)3 or BF3ˇOEt2, by a variety of allyl nucleophiles affords homopropargylic
homoallylic alcohols in good yield and selectivity. Subsequent enyne metathesis
gives functionalized vinylcyclopentenols.
L. Wang, M. L. Maddess, M. Lautens, J. Org. Chem., 2007,
72, 1822-1825.
In a new, efficient, catalytic asymmetric protocol for the synthesis of
α-tertiary hydroxyaldehydes from readily available α-halo or α-hydroxy ketones
or enol silyl ethers, the chiral ligand controls the regioselectivity as well as
the enantioselectivity.
B. M. Trost, J. Xu, M. Reichle, J. Am. Chem. Soc., 2007,
129, 282-283.
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.
3-Substituted-2-alkoxycarbonyl allylboronates are readily produced by
the cross-coupling of Baylis-Hillman acetate adducts and
bis(pinacolato)diboron in the presence of palladium catalyst. Subsequent
addition of excess aqueous KHF2 gives stable allyl
trifluoroborate salts. Allylboronate and allyltrifluoroborate derivatives
may react stereoselectively with aldehydes to afford functionalized
homoallylic alcohols.
G. W. Kabalka B. Venkataiah, G. Dong, J. Org. Chem., 2004,
69, 5807-5809.
A highly regioselective vinylogous aldol reaction catalyzed by SiCl4
and a chiral phosphoramide, provides δ-hydroxy enones for a variety of
aldehyde and dienol ether structures in good yields, excellent
enantioselectivities, and in some cases excellent anti
diastereoselectivities.
S. E. Denmark, G. L. Beutner, J. Am. Chem. Soc., 2003,
125, 7800-7801.
The weakly acidic species, silicon tetrachloride (SiCl4), can be
activated by binding of a strongly Lewis basic chiral phosphoramide, leading
to in situ formation of a chiral Lewis acid for catalysis of the aldol
reaction of silyl ketene acetals and silyl dienol ethers (vinylogous aldol
reactions) to conjugated and nonconjugated aldehydes. The high levels of
regio-, anti
diastereo-, and enantioselectivity observed are discussed.
S. E. Denmark, G. L. Beutner, T. Wynn, M. D. Eastgate, J. Am. Chem. Soc.,
2005,
127, 3774-3789.
N,O-Silyl dienyl ketene acetals are useful reagents for highly
enantioselective vinylogous aldol additions to various aldehydes in the
presence of SiCl4 and the catalytic action of a chiral
phosphoramide.
S. E. Denmark, J. R. Heemstra, Jr., J. Am. Chem. Soc.,
2006,
128, 1038-1039.
Highly diastereo- and enantioselective syntheses of 1,5-disubstituted (E)-1,5-anti-pent-2-endiols
and (Z)-1,5-syn-pent-2-endiols have been achieved via the
one-pot coupling of two different aldehydes with bifunctional
γ-boryl-substituted allylborane reagents, which were generated in situ by
the hydroboration of allenes with diisopinocampheylborane. The
stereospecificity is discussed.
E. M. Flamme, W. R. Roush, J. Am. Chem. Soc., 2002,
124, 13644-13645.
A highly regio- and stereoselective palladium-catalyzed synthesis of various
2-silylallylboronates from allenes and
2-(dimethylphenylsilanyl)-4,4,5,5-tetramethyl[1,3,2]dioxaborolane afforded
the corresponding silaboration products in moderate to excellent yields. In
the absence of an organic iodide, the silaboration gives products having
completely different regiochemistry. In the presence of an aldehyde, the
silaboration reaction afforded homoallylic alcohols in one pot in good to
excellent yields, with exceedingly high syn selectivity.
K.-J. Chang, D. K. Rayabarapu, F.-Y. Yang, C.-H. Cheng, J. Am. Chem. Soc.,
2005,
127, 126-131.
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Enantioselective Allylic Carbon-Carbon Bond Construction |
