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Synthesis of homoallylic alcohols


Name Reactions

Alder-Ene Reaction

Hosomi-Sakurai Reaction

Hosomi-Sakurai Reaction

Nozaki-Hiyama Coupling

[2,3]-Wittig Rearrangement

Recent Literature

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.

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.

Chiral phosphoric acids catalyze an enantioselective addition of bi(cyclopentyl)diol-derived boronates to aldehydes to provide homoallylic, propargylic, and crotylic alcohols with high enantiomeric excess and diastereomeric ratios. A wide substrate scope was exhibited, and the novel boronates provided high enantiocontrol.
J. Yuan, P. Jain, J. C. Antilla, J. Org. Chem., 2020, 85, 12988-13003.

C2-symmetric chiral-substituted 1,16-dihedroxytetraphenylenes (DHTP) were used as organocatalysts in asymmetric allylboration of ketones under very mild conditions. Several tertiary alcohols were isolated in good yields with high ees.
G.-L. Chai, B. Zhu, J. Chang, J. Org. Chem., 2019, 84, 120-127.

A general allylation of a diverse array of ketones with allyl boronates is effective with 2 mol % of a zinc alkoxide catalyst and with relatively short reaction times. Studies of the key exchange process are presented, which support a cyclic transition state for the boron to zinc exchange.
K. R. Fandrick, D. R. Fandrick, J. J. Gao, J. T. Reeves, Z. Tan, W. Li, J. J. Song, B. Lu, N. K. Yee, C. H. Senanayake, Org. Lett., 2010, 12, 3748-3751.

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.

A ball-milling-enabled zinc-mediated Barbier-type allylation of a broad range of carbonyl compounds is operationally simple and does not require inert atmospheres or dry solvents. The reaction is applicable across a range of different zinc metal morphologies.
J. Yin, R. T. Stark, I. A. Fallis, D. L. Browne, J. Org. Chem., 2020, 85, 2347-2354.

An expanded survey of transition-metal catalysts has confirmed that cobalt salts uniquely deliver homoallylic alcohol products from epoxides, with retention of the original epoxide stereochemistry. A tandem Corey-Chaykovsky/epoxide olefination sequence gives homoallylic alcohols from aldehydes.
M. L Jamieson, N. Z. Brant, M. A. Brimble, D. P. Furkert, Synthesis, 2017, 49, 3952-3956.

A cationic iridium complex-catalyzed olefin transposition of (E)-1-alkenylboronates followed by a chiral phosphoric acid-catalyzed allylation reaction of aldehydes enables a highly diastereo- and enantioselective synthesis of anti homoallylic alcohols.
T. Miura, Y. Nishida, M. Morimoto, M. Murakami, J. Am. Chem. Soc., 2013, 135, 11497-11500.

A nickel complex catalyzes an allylboration of aldehydes, facilitating the preparation of homoallylic alcohols in high diastereoselectivity. Allylation occurs through a well-defined six-membered transition state, with nickel acting as a Lewis acid.
F. M. Dennis, C. C. Robertson, B. M. Partridge, Synthesis, 2020, 52, 1903-1914.

A highly reactive nickel-catalyst system enables an in situ transposition of a homoallyl pinacol boronic ester to a Z-crotyl pinacol boronic ester, that reacts with various aldehydes to form syn-homoallylic alcohols in high diastereoselectivities. Also, the multiple transposition of pentenyl pinacol boronic ester was realized.
F. Weber, M. Ballmann, C. Kohlmeyer, G. Hilt, Org. Lett., 2016, 18, 548-551.

1,4-Pentadiene and 1,5-hexadiene can serve as allylmetal pronucleophiles in regio-, anti-diastereo-, and enantioselective carbonyl additions from alcohol proelectrophiles. Primary alcohol dehydrogenation delivers a ruthenium hydride that affects alkene isomerization to furnish a conjugated diene, followed by transfer hydrogenative carbonyl addition.
Z. J. Dubey, W. Shen, J. A. Little, M. K. Krische, J. Am. Chem. Soc., 2023, 145, 8576-8582.

An unprecedented cobalt-catalyzed highly site-, diastereo-, and enantioselective protocol for stereoselective formation of nucleophilic allyl-Co(II) complexes followed by addition to aldehydes provides diversified enantioenriched homoallylic alcohols with a remarkably broad scope of allyl groups that can be introduced.
L. Wang, L. Wang, M. Li, Q. Chong, F. Meng, J. Am. Chem. Soc., 2021, 143, 12755-12765.

A highly diastereoselective Pd-catalyzed carbonyl allylation of aldehydes and isatins with simple acyclic olefins as allylating reagents consists of a Pd-catalyzed oxidative allylic C-H borylation and an allylboration of carbonyls accelerated by phosphoric acid. N-Fluorobenzenesulfonimide as oxidant plays a key role.
Z.-L. Tao, X.-H. Li, Z.-Y. Han, L.-Z. Gong, J. Am. Chem. Soc., 2015, 137, 4054-4057.

Chiral ruthenium(II) complexes catalyze a highly regio-, diastereo-, and enantioselective reaction of alkynes with primary alcohols to form homoallylic alcohols. In this enantioselective carbonyl allylation, alkynes serve as allylmetal equivalents.
T. Liang, K. D. Ngyuen, W. Zhang, M. J. Krische, J. Am. Chem. Soc., 2015, 137, 3161-3164.

In RuI(CO)(η3-C3H5)(JOSIPHOS) catalyzed anti-diastereo- and enantioselective C-C couplings of primary alcohols with 1-aryl-1-propynes, a non-classical hydrogen bond between iodide and the aldehyde formyl CH bond stabilizes the favored transition state for carbonyl addition. An improved catalytic system provides previously unattainable products of carbonyl anti-(α-aryl)allylation.
E. Ortiz, J. Z. Shezaf, Y.-H. Chang, T. P. Gonçalves, K.-W. Huang, M. J. Krische, J. Am. Chem. Soc., 2021, 143, 16709-16717.

The photoexcitation of Hantzsch ester can directly activate chromium reagents through a single-electron transfer process. The synthetic application was demonstrated through a photoredox decarboxylative allylation of aldehydes with feedstock butadiene without exogenous photocatalysts, metallic reductants, or additives.
S. Lin, Y. Chen, H. Yan, Y. Liu, Y. Sun, E. Hao, C. Shi, D. Zhang, N. Zhu, L. Shi, Org. Lett., 2021, 23, 8077-8081.

Enantioselective transfer hydrogenation of 1,1-dimethylallene in the presence of aldehydes and 2-propanol or primary alcohols without 2-propanol employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, m-nitrobenzoic acid, and (S)-SEGPHOS delivers reverse-prenylation products in very good yields and enantioselectivities.
S. B. Han, I. S. Kim, H. Han, M. J. Krische, J. Am. Chem. Soc., 2009, 131, 6916-6917.

General In(0)-catalyzed allylations of ketones proceeded smoothly in water under mild conditions, and water proved to be essential for these reactions. Both the substrate scope and the functional group tolerance were excellent. The In metal catalyst could be easily recovered and reused without loss of catalytic activity.
U. Schneider, M. Ueno, S. Kobayashi, J. Am. Chem. Soc., 2008, 130, 13824-13825.

γ-Adducts of homoallylic alcohols were converted to the corresponding α-adducts by an acid-catalyzed allyl-transfer reaction. In the allyl-transfer reaction, anti- and syn-γ-adducts gave E- and Z-α-adducts, respectively, and the optical purity was transferred to the α-adducts This suggests that the allyl-transfer reaction proceeds stereoselectively via a six-membered cyclic transition state.
S.-i. Sumida, M. Ohga, J. Mitani, J. Nokami, J. Am. Chem. Soc., 2000, 122, 1310-1313.

Nickel catalyzes a multicomponent coupling reaction of terminal alkenes, carbon dioxide, and organoaluminum reagents to provide homoallylic alcohols in good yields with excellent regio- and stereoselectivities.
Y. Mori, C. Shigeno, Y. Luo, B. Chan, G. Onodera, M. Kimura, Synlett, 2018, 29, 742-746.

A practical Ni(cod)-catalyzed three-component coupling of 1,3-butadiene, carbonyl compounds, and arylboronic acids provides 1,4-disubstituted homoallylic alcohols without any external base and ligand at ambient temperature. The neutral conditions tolerate even highly base-sensitive functional groups.
Y.-Q. Li, G. Chen, S.-L. Shi, Org. Lett., 2021, 23, 2571-2577.

A Ni-catalyzed three-component cross-electrophile coupling of 1,3-dienes with aldehydes and aryl bromides using manganese metal as the reducing agent provides 1,4-disubstituted homoallylic alcohols.
Y.-Q. Qi, S. Liu, Y. Xu, Y. Li, T. Su, H.-L. Ni, Y. Gao, W. Yu, P. Cao, P. Hu, K.-Q. Zhao, B.-Q. Wang, B. Chen, Org. Lett., 2022, 24, 5023-5028.

A highly selective copper-catalyzed reductive hydroxymethylation of 1,3-dienes with CO2 provides chiral all-carbon acyclic quaternary stereocenters. A variety of readily available 1,1-disubstituted 1,3-dienes, as well as a 1,3,5-triene, undergo the reaction with high chemo-, regio-, E/Z-, and enantioselectivities and good functional group tolerance.
X.-W. Chen, L. Zhu, Y.-Y. Gui, K. Jing, Y.-X. Jiang, Z.-Y. Bo, Y. Lan, J. Li, D.-G. Yu, J. Am. Chem. Soc., 2019, 141, 18825-18835.

The use of montmorillonite clay as catalyst provides a straightforward and scalable, highly diastereoselective method for the allylation and crotylation of a range of ketones and aldehydes with air- and water-stable potassium allyl and crotyltrifluoroborate salts.
F. Nowrouzi, A. N. Thadani, R. A. Batey, Org. Lett., 2009, 11, 2631-2634.

Insertion of 2-substituted dienes into the methanol C-H bond occurs in a regioselective manner to form all-carbon quaternary centers with excellent levels of enantioselectivity using an iridium-PhanePhos catalyst via methanol dehydrogenation, reversible diene hydrometalation, and regioisomeric formation of allyliridium-formaldehyde pairs.
K. D. Nguyen, D. Herkommer, M. J. Krische, J. Am. Chem. Soc., 2016, 138, 14210-14213.

(R,R)-Ph-BPE ligated Cu catalyzes a chemo-, regio-, and enantioselective allylation of ketones with 1,3-dienes in the presence a hydrosilane to provide chiral homoallylic tertiary alcohols under very mild conditions with good functional group tolerance. 1,3-dienes as the latent allylic nucleophiles avoid the the use of stoichiometric quantities of allylmetal reagents.
B. Fu, X. Yuan, Y. Li, Y. Wang, Q. Zhang, T. Xiong, Q. Zhang, Org. Lett., 2019, 21, 3576-3580.

A combined carbocupration of terminal alkynes followed by a zinc homologation and further reaction with ketones lead, in a single-pot operation, to homoallylic alcohols possessing two consecutive quaternary stereocenters with excellent diastereoselectivity.
B. Dutta, N. Gilboa, I. Marek, J. Am. Chem. Soc., 2010, 132, 5588-5589.

Asymmetric allylation of aldehydes with γ-disubstituted allyl halides in the presence of a sulfonamide/oxazoline chromium complex provides various synthetically useful α-homoallylic alcohols with two consecutive stereogenic centers, including one quaternary carbon, in a highly diastereoselective and enantioselective manner.
Y. Xiong, G. Zhang, Org. Lett., 2016, 18, 5094-5097.

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.

Under catalysis by ruthenium trichloride in the presence of carbon monoxide, water, and triethylamine, a wide range of aromatic, olefinic, and aliphatic aldehydes are efficiently allylated with allyl acetate under mild conditions. The stoichiometric byproducts of this reaction are carbon dioxide and acetic acid.
S. E. Denmark, S. T. Nguyen, Org. Lett., 2009, 11, 781-784.

An iridium-catalyzed coupling of 1-aryl-1-propynes with primary alcohols gives secondary homoallylic alcohols as products. This reaction involves an iridium-catalyzed novel catalytic transformation of 2-alkynes and primary alcohols through the formation of hydrido(π-allyl)iridium as a possible key intermediate.
Y. Obora, S. Hatanaka, Y. Ishii, Org. Lett., 2009, 11, 3510-3513.

Titanocene dichloride catalyzes the formation of an organozinc species via catalytic activation of allyl halides. Nucleophilic addition to carbonyl derivatives provides the desired homoallylic alcohols in very good yields in short reaction times. This discovery will have wide ranging applicability in the generation of highly reactive organometallic reagents.
L. M. Fleury, B. L. Ashfeld, Org. Lett., 2009, 11, 5670-5673.

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.

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.

A solvent- and metal-free process for the direct methallylboration of ketones with a stable B-methallylborinane is accelerated by tertiary alcohols. In the presence of 2.0 equiv of tert-amyl alcohol, the methallylation products were prepared at room temperature in excellent yields. The process offers simple operation, high efficiency, and mild reaction conditions.
Y. Zhang, N. Li, N. Goyal, G. Li, H. Lee, B. Z. Lu, C. H. Senanayake, J. Org. Chem., 2013, 78, 5775-5781.

The combination of Bi(OAc)3 and a chiral phosphoric acid catalyzes a highly efficient asymmetric 1,2-allylation reaction of β,γ-unsaturated α-ketoesters under mild conditions. A subsequent anionic oxy-Cope rearrangement achieves an asymmetric formal 1,4-allylation reaction in a one-pot process.
X.-S. Liu, Y. Li, X. Li, Org. Lett., 2021, 23, 9128-9133.

Cu-catalyzed highly regio- and stereoselective 1,4-protoboration of dienylboronates provides unsymmetrical 1,4-bifunctional allylboron reagents. A subsequent chemoselective allylboration with aldehydes followed by oxidative workup give diol products with high diastereoselectivity.
S. Gao, M. Wang, M. Chen, Org. Lett., 2018, 20, 7921-7925.

An enantioselective nickel-catalyzed borylative coupling of 1,3-dienes with aldehydes provides an efficient route to highly valuable homoallylic alcohols in a single step. Enabled by a chiral spiro phosphine-oxazoline nickel complex, this transformation yields products with exceptional diastereoselectivity, E-selectivity, and enantioselectivity.
J.-T. Ma, T. Zhang, B.-Y. Yao, L.-J. Xiao, Q.-L. Zhou, J. Am. Chem. Soc., 2023, 145, 19195-19201.

An enantioselective nickel-catalyzed borylative coupling of 1,3-dienes with aldehydes provides an efficient route to highly valuable homoallylic alcohols in a single step. Enabled by a chiral spiro phosphine-oxazoline nickel complex, this transformation yields products with exceptional diastereoselectivity, E-selectivity, and enantioselectivity.
J.-T. Ma, T. Zhang, B.-Y. Yao, L.-J. Xiao, Q.-L. Zhou, J. Am. Chem. Soc., 2023, 145, 19195-19201.

A chiral α-borylmethyl-(Z)-crotylboronate reagent enables highly stereo- and enantioselective syntheses of (E)-δ-hydroxymethyl-syn-homoallylic alcohols via aldehyde allylboration and a subsequent oxidative workup.
J. Liu, S. Gao, M. Chen, Org. Lett., 2021, 23, 9451-9456.

Racemic homoallenyl alcohols can be synthesized from aldehydes and chloroprene-derived Grignards. The use of bis[2-dimethylaminoethyl]ether (BDMAEE) as an additive at low temperatures shifts the selectivity of the reaction almost exclusive toward allene formation. Simple and more elaborate methods for further derivatization enable quick access to more complex structures.
A. G. A. Geissler, B. Breit, Org. Lett., 2021, 23, 2621-2625.

Cu-catalyzed allylation of aldehydes or ketones with α-vinyl allylboronate provides secondary or tertiary δ-vinyl-homoallylic alcohols with high E-selectivities. It is proposed that the reaction operates under the Curtin-Hammett principle via the intermediacy of an α-vinyl allylic copper species.
J. Liu, B. Su, M. Chen, Org. Lett., 2021, 23, 6035-6040.

Copper(I) catalyzes a regioselective asymmetric allylation of ketones with commercially available 1,4-pentadiene as a pronucleophile to provide a variety of chiral tertiary alcohols bearing a terminal (Z)-1,3-diene in high (Z)/(E) ratio and high enantioselectivity. The synthetic utility of the product is demonstrated by a copper(I)-catalyzed regioselective borylation of the 1,3-diene group.
F. Zhong, Z.-Z. Pan, S.-W. Zhou, H.-Jun. Zhang, L. Yin, J. Am. Chem. Soc., 2021, 143, 4556-4562.

A regio- and stereoselective nickel-catalyzed three-component coupling reaction of aldehydes, 1,3-dienes, and alkenylzirconium afforded skipped diene compounds bearing various functionals and heterocyclic groups. The products were readily transformed into structurally diverse polyenes.
C.-G. Wang, Y. Zhang, S. Wang, B. Chen, Y. Li, H.-L. Ni, Y. Gao, P. Hu, B.-Q. Wang, P. Cao, Org. Lett., 2021, 23, 535-541.

An In(III)-catalyzed intermolecular glyoxylate-ene reaction enables an efficient synthesis of homoallylic alcohols with high enantioselectivities and anti-diastereoselectivities. Only alkene isomers having a proton β-cis to the substituent reacted in this catalytic system.
X. Zhang, M. Wang, R. Ding, Y.-H. Xu, T.-P. Loh, Org. Lett., 2015, 17, 2736-2739.

In situ generation of allylic boronates by iridium-catalyzed borylation of cyclic alkenes in the presence of additives, such as methylimidazole and DBU, followed a reaction with aldehydes allows the synthesis of stereodefined homoallylic alcohols. Cycloalkenes without additives as well as acyclic substrates gave vinylic boronates, which were coupled with organohalides in a Suzuki-Miyaura sequence.
V. J. Olsson, K. J. Szabó, J. Org. Chem., 2009, 74, 7715-7723.

A regio- and diastereoselective nickel-catalyzed reductive coupling of carbonyls with dienes in the presence of a stoichiometric amount of bis(pinacolato)diboron furnishes allyl boronic esters as the reaction product, which was readily converted to the derived allylic alcohol by oxidative workup.
H. Y. Cho, J. P. Morken, J. Am. Chem. Soc., 2008, 130, 16140-16141.

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.

The palladium catalyzed decarboxylative asymmetric allylic alkylation of allyl 1,2-enediol carbonates gives exclusively α-hydroxyketones in very good yields and high enantiomeric excesses using Lnaph as ligand in DME. The reaction proceeds under extremely mild conditions and tolerates a broad range of esters.
B. M. Trost, J. Xu, T. Schmidt, J. Am. Chem. Soc., 2008, 130, 11852-11853.

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.

Highly stereoselective 2-oxonia-Cope rearrangement reactions between rationally designed nonracemic vinylogous aldolation synthons and aldehydes provide δ-hydroxy-α,β-unsaturated esters with excellent enantioselectivities and unprecedented Z- and E-selectivities.
A. Padarti, H. Han, Org. Lett., 2018, 20, 1448-1452.

Highly stereoselective 2-oxonia-Cope rearrangement reactions between rationally designed nonracemic vinylogous aldolation synthons and aldehydes provide δ-hydroxy-α,β-unsaturated esters with excellent enantioselectivities and unprecedented Z- and E-selectivities.
A. Padarti, H. Han, Org. Lett., 2018, 20, 1448-1452.

A novel nickel(II)-N,N′-dioxide complex facilitated the asymmetric synthesis of biologically interesting α-hydroxy carbonyl compounds under mild conditions by highly enantioselective carbonyl-ene reactions of glyoxal derivatives with various alkenes. Various aromatic, aliphatic, and heteroaromatic glyoxal derivatives, as well as glyoxylate, were tolerated.
K. Zheng, J. Shi, X. Liu, X. Feng, J. Am. Chem. Soc., 2008, 130, 15770-15771.

Highly enantioselective carbonyl-ene reactions of various 1,1-disubstituted and trisubstituted alkenes with ethyl glyoxylate are catalyzed by a new Co-salen complex under nearly ideal conditions at room temperature using low catalyst loadings. The reaction provides chiral, homoallylic alcohol products in excellent yields, enantioselectivities, and diastereoselectivities.
G. E. Hutson, A. H. Dave, V. H. Rawal, Org. Lett., 2007, 9, 3869-3872.

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 a palladium catalyst. Subsequent addition of excess aqueous KHF2 gives stable allyl trifluoroborate salts. Allylboronate and allyltrifluoroborate derivatives 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.

Addition of α-alkenylzirconacyclopentenes to aldehyde enables a highly stereoselective synthesis of β-hydroxyallenes with multiple stereogenic centers including allenic axial chirality, as well as center chirality. Remarkably, the reaction occurs with completely different chemoselectivity in comparison with the usual alkyl- or aryl-substituted zirconacyclopentenes.
Y. Zhou, J. Chen, C. Zhao, E. Wang, Y. Liu, Y. Li, J. Org. Chem., 2009, 74, 5326-5330.

A nucleophilic allylation of acylsilanes in water provides versatile functionalized tertiary α-silyl alcohols in high yields with the assistance of hydrogen bonding. Unlike the conventional strategy, transition metals and an additional Lewis acid catalyst were not required.
X.-X. Liang, C. Zhu, W. Zhang, Y.-N. Du, L. Xu, L. Liu, Y. Zhang, M.-Y. Han, J. Org. Chem., 2023, 88, 12087-12099.

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