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Synthesis of homoallylic alcohols

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Alder-Ene Reaction


Hosomi-Sakurai Reaction


Hosomi-Sakurai Reaction


Nozaki-Hiyama Coupling


[2,3]-Wittig Rearrangement


Recent Literature


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.

Enantioselective Allylic Carbon-Carbon Bond Construction