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Allylic Substitutions, Allylation


Name Reactions

Claisen Rearrangement

Ene Reaction

Ireland-Claisen Rearrangement

Hosomi-Sakurai Reaction

Hosomi-Sakurai Reaction

Recent Literature

Nickel-Catalyzed Asymmetric Negishi Cross-Couplings of Secondary Allylic Chlorides with Alkylzincs
S. Son, G. C. Fu, J. Am. Chem. Soc., 2008, 130, 2756-2757.

The reaction of secondary and tertiary alkyl halides with benzylic or allylic Grignard reagents in the presence of a catalytic amount of silver nitrate in ether yielded the corresponding cross-coupling products in high yields. The coupling reaction provides efficient access to quaternary carbon centers.
H. Someya, H. Ohmiya, H. Yorimitsu, K. Oshima, Org. Lett., 2008, 10, 969-971.

Boron "ate" complexes derived from pinacol boronic esters and tert-butyl lithium undergo stereospecific transmetalation to copper cyanide, followed by coupling with alkynyl bromides, allyl halides, propargylic halides, β-haloenones, hydroxylamine esters, and acyl chlorides. This simple transformation converts primary and secondary alkylboronic esters to a wide array of useful compounds.
N. Xu, H. Liang, J. P. Morken, J. Am. Chem. Soc., 2022, 144, 11546-11552.

The use of Ni(dppe)Cl2 as catalyst resulted in the cross-coupling of allylic alcohols with primary alkyl Grignard reagents and cyclopropylmagnesium bromide, whereas Ni(PCy3)2Cl2 and dcype led to the reduction of allylic alcohols in the presence of alkyl Grignard reagents. Secondary alkyl Grignard reagents except cyclopropylmagnesium bromide always led to reduction of allylic alcohols.
B. Yang, Z.-X. Wang, J. Org. Chem., 2020, 85, 4772-4784.

Electrochemistry enables smooth Zn-mediated allylic alkylations in aqueous media under air in the presence of a Pd catalyst between a full range of alkyl halides (primary, secondary, and tertiary) and substituted allylic halides.
Y.-L. Lai, J.-M. Huang, Org. Lett., 2017, 19, 2022-2025.

Photoredox/nickel dual catalysis enables a radical-mediated functionalization of allyl alcohol (derivatives) with a variety of alkyl 1,4-dihydropyridines with high linear and E-selectivity. This reaction avoids harsh conditions (e.g., strong base, elevated temperature). Additionally, using aryl sulfinate salts as radical precursors, allyl sulfones can also be obtained.
Z.-J. Wang, S. Zheng, E. Romero, J. K. Matsui, G. A. Molander, Org. Lett., 2019, 21, 6543-6547.

Efficient enantioselective Cu-catalyzed alkylations of aromatic and aliphatic allylic phosphates bearing di- and trisubstituted olefins are promoted in the presence of a readily available chiral amino acid-based ligand. Tertiary and quaternary stereogenic carbon centers are delivered regioselectively in high ee.
M. A. Kacprzynski, A. H. Hoveyda, J. Am. Chem. Soc., 2004, 126, 10676-10681.

TiCl4 efficiently promotes the replacement of hydroxyl groups in tertiary, benzylic, and allylic alcohols, and even nonactivated secondary alcohols, by an allyl group in high yields. The reaction usually proceeds within minutes at room temperature.
A. Hassner, C. R. Bandi, Synlett, 2013, 24, 1275-1279.

Direct Csp3−Csp3 coupling of various aliphatic trimethylsilyl ethers and allylsilanes is effectively catalyzed by InCl3 and I2. The transformation probably involves an in situ-derived combined Lewis acid of InCl3 and Me3SiI. The reaction allows the construction of quaternary-quaternary and quaternary-tertiary carbon-carbon bonds and tolerates aryl halide moieties.
T. Saito, Y. Nishimoto, M. Yasuda, A. Baba, J. Org. Chem., 2007, 72, 8588-8590.

A Cu-catalyzed cross-coupling reaction of allyl boron ester with halogenated alkanes provides a mild and efficient method for the construction of saturated C(sp3)-C(sp3) bonds. This protocol works with nonactivated primary, secondary, and even tertiary halogenated alkanes under mild conditions.
G.-Z. Wang, J. Jiang, X.-S. Bu, J.-J. Dai, J. Xu, Y. Fu, H.-J. Xu, Org. Lett., 2015, 17, 3682-3685.

Sarcosine is an excellent ligand for cobalt-catalyzed carbon-carbon cross-coupling of Grignard reagents with allylic and vinylic bromides. The system performs efficiently when phenyl and benzyl Grignards are coupled with alkenyl bromides. Notably, previously unachievable Co-catalyzed coupling of allylic bromides with Grignards to linearly coupled α-products was also realized.
R. Frlan, M. Sova, S. Gobec, G. Stavber, Z. Časar, J. Org. Chem., 2015, 80, 7803-7809.

A promising new approach to a generalized allylation process uses various easily accessible allyl diphenylphosphine oxides as radical trapping agents for the allylation of ditihocarbonates.
G. Ouvry, B. Quiclet-Sire, S. Z. Zard, Angew. Chem. Int. Ed., 2006, 45, 5002-5006.

The palladium-catalyzed reaction of allyl acetates with aryl- and vinyltin reagents gave good yields of cross-coupled products. The reaction was mild and tolerant of functionality (-CO2R, -OH, -OSiR3, -OMe) in the tin reagent. Inversion of stereochemistry at the acetate center was observed, with retention of the geometry of the olefin of the allyl group and with exclusive coupling at the primary position. Retention of geometry of the olefin in the vinyltin reagents was also observed.
L. Del Valle, J. K. Stille, L. S. Hegedus, J. Org. Chem, 1990, 55, 3019-3023.

The Pd(0)-catalyzed allylic cross-coupling of homoallylic tosylate substrates using boronic acids and pinacol esters uses 2-(4,5-dihydro-2-oxazolyl)quinoline (quinox) as a ligand and is performed at ambient temperature. The scope of the reaction is broad in terms of both the boronate and the tosylate, that includes secondary tosylates.
B. J. Stokes, S. M. Opra, M. S. Sigman, J. Am. Chem. Soc., 2012, 134, 11408-11411.

B(C6F5)3 catalyzes a highly effective allylation of secondary benzylic alcohol derivatives with allylsilanes. The reaction tolerates a broad range of additional functionalities, such as bromo, acetoxy, and primary benzyloxy groups.
M. Rubin, V. Gevorgyan, Org. Lett., 2001, 3, 2705-2707.

In a Pd-catalyzed cross-coupling of aromatic and aliphatic allylic carbonates and allylB(pin), small-bite-angle ligands favor the branched substitution product. This mode of regioselection is consistent with a reaction that operates by a 3,3′ reductive elimination reaction. In the presence of appropriate chiral ligands, this reaction is rendered enantioselective.
P. Zhang, L. A. Brozek, J. P. Morken, J. Am. Chem. Soc., 2010, 132, 10686-10688.

Carreira's iridium-(P, olefin) phosphoramidite-based catalytic system enables an asymmetric allyl-allylboronate cross-coupling with high enantioselectivity. This transformation tolerates a large variety of racemic branched allylic alcohols and allylboronate substrates. The utility of the coupling is demonstrated in a concise catalytic asymmetric synthesis of (-)-preclamol.
Y. Zheng, B.-B. Yue, K. Wei, Y.-R. Yang, Org. Lett., 2018, 20, 8035-8038.

Optimized reaction conditions expand the scope of Pd-catalyzed allyl-allyl couplings to allow the generation of 1,5-dienes with tertiary centers adjacent to quaternary centers as well as a unique set of cyclic structures. Using a chiral bidentate diphosphine ligand, the asymmetric cross-coupling of allylboron reagents and allylic electrophiles establishes 1,5-dienes with adjacent stereocenters in high regio- and stereoselectivity.
M. J. Ardolino, J. P. Morken, J. Am. Chem. Soc., 2014, 136, 7092-7100.

A palladium-catalyzed cross-coupling of allyl boronates and chiral propargyl acetates delivers chiral 1,5-enynes with excellent levels of chirality transfer. The reaction can be applied across a broad range of substrates.
M. J. Ardolino, J. P. Morken, J. Am. Chem. Soc., 2012, 134, 8770-8773.

A highly enantioselective Sonogashira type synergistic Rh and Cu catalysis of readily available terminal alkynes and racemic allylic carbonates provides branched 1,4-enynes under neutral conditions. Aliphatic and aromatic terminal alkynes with various functional groups could be used directly.
W.-Y. Huang, C.-H. Lu, S. Ghorai, B. Li, C. Li, J. Am. Chem. Soc., 2020, 142, 15276-15281.

A direct dehydrative coupling of terminal alkynes with allylic alcohols is catalyzed by Pd(PPh3)4 in the presence of an N,P-ligand and Ti(OiPr)4. The coupling reaction tolerates various functional groups and provides a valuable synthetic tool to access 1,4-enynes.
Y.-X. Li, Q.-Q. Xuan, L. Liu, D. Wang, Y.-J. Chen, C.-J. Li, J. Am. Chem. Soc., 2013, 135, 12536-12539.

An iridium-catalyzed stereoselective coupling of allylic ethers and alkynes provides 3,4-substituted 1,5-enynes with excellent regio-, diastereo-, and enantioselectivities, and the protocol is functional group tolerant. Moreover, conditions are reported that allow the reaction to proceed with complete reversal of diastereoselectivity.
J. Zhu, Y. Wang, A. D. Charlack, Y.-M. Wang, J. Am. Chem. Soc., 2022, 144, 15480-15487.

A neighboring boronate group in vicinal bis(boronic esters) provides a dramatic rate acceleration in transmetalation to copper and thereby enables unprecedented site-selective cross-couplings  allyl, alkynyl, and propargyl electrophiles as well as a simple proton. This cross-coupling operates under practical experimental conditions.
N. Xu, Z. Kong, J. Z. Wang, G. J. Lovinger, J. P. Morken, J. Am. Chem. Soc., 2022, 144, 17815-17823.

Metalation of 3-methyl-3-buten-1-ol with n-BuLi in the presence of TMEDA followed by treatment of the resulting dianion with alkyl halides is a general route to 3-methylene-1-alkanols. This chemistry could be used advantageously for the preparation of butyrolactone, pyranol, stinkbug pheromone, topostin, and γ-geraniol precursors.
K. H. Yong, J. A. Lotoski, J. M. Chong, J. Org. Chem., 2001, 66, 8248-8251.

An efficient Ni-catalyzed reductive carboxylation of brached and linear allylic alcohols with CO2 provides linear β,γ-unsaturated carboxylic acids as the sole regioisomer with generally high E/Z stereoselectivity. In addition, the carboxylic acids can be generated from propargylic alcohols via a hydrogenation step made possible by a Ni hydride intermediate produced by a hydrogen atom transfer from water.
Y.-G. Chen, B. Shuai, C. Ma, X.-J. Zhang, P. Fang, T.-S. Mei, Org. Lett., 2017, 19, 2969-2972.

In the presence of a Cu(I)/NHC catalyst, highly regioselective reactions of allylboronic pinacol esters with CO2 (1 atm) give exclusively the more substituted β,γ-unsaturated carboxylic acids in most cases. Various substituted carboxylic acids can be prepared via this method, including compounds featuring all-carbon quaternary centers.
H. A. Duong, P. B. Huleatt, Q.-W. Tan, E. L. Shuying, Org. Lett., 2013, 15, 4034-4037.

Exposure of N-acyloxyphthalimides (redox-active esters) to galvanostatic electroreductive conditions enables a general regio- and stereoselective alkylation of Morita-Baylis-Hillman compounds in high yields. The method offers wide functional group tolerance.
G. Bertuzzi, G. Ombrosi, M. Bandini, Org. Lett., 2022, 24, 4354-4359.

A Ni-catalyzed regiodivergent reductive carboxylation of allyl esters with CO2 is mild, user-friendly, and operationally simple. The reaction is characterized by an exquisite selectivity profile that is dictated by the ligand backbone.
T. Moragas, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 17702-17705.

A Ni-catalyzed regiodivergent reductive carboxylation of allyl esters with CO2 is mild, user-friendly, and operationally simple. The reaction is characterized by an exquisite selectivity profile that is dictated by the ligand backbone.
T. Moragas, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 17702-17705.

A direct, palladium-catalyzed, carbonylative transformation of allylic alcohols in the presence of formic acid as the CO source provides β,γ-unsaturated carboxylic acids with excellent linear and (E)-selectivity under mild conditions.
F.-P. Wu, J.-B. Peng, L.-Y. Fu, X. Qi, X.-F. Wu, Org. Lett., 2017, 19, 5474-5477.

An addition of tertiary carbon radicals generated by an Ir-catalyzed visible-light photocatalyst to electron-deficient 1,3-dienes proceeds in good yields. The reaction appends a δ-substituted β,γ-unsaturated carbonyl fragment to a tertiary alcohol or carboxylic acid precursor and constructs a new quaternary carbon center.
S. Y. Abbas, P. Zhao, L. E. Overman, Org. Lett., 2018, 20, 868-871.

Formate salts can serve as hydride as well as a CO2 source in a mild PGeP-palladium complex-catalyzed hydrocarboxylation of allenes through a highly efficient decarboxylation-carboxylation process.
C. Zhu, J. Takaya, N. Iwasawa, Org. Lett., 2015, 17, 1814-1817.

With K2S2O8 as the oxidant and AgNO3 as the catalyst, direct decarboxylative radical allylation of aliphatic carboxylic acids with allyl sulfones in aqueous CH3CN solution gave the corresponding alkenes in good yields under mild conditions. This site-specific allylation method exhibits wide functional group compatibility.
L. Cui, H. Chen, C. Liu, C. Li, Org. Lett., 2016, 18, 2188-2191.

Morita-Baylis-Hillman Reaction of α,β-Unsaturated Ketones with Allylic Acetates by the Combination of Transition-Metal Catalysis and Organomediation
Y.-Q. Li, H.-J. Wang, Z.-Z. Huang, J. Org. Chem., 2016, 81, 4429-4433.

A Ni-catalyzed reductive allylation of α-chloroboronates with allyl sulfones efficiently provides the corresponding homoallylic boronates, which could be readily converted into valuable homoallylic alcohols or amines or 1,4-diboronates. This reaction features a broad substrate scope with good functional group compatibility.
Y. Lou, J. Qiu, K. Yang, F. Zhang, C. Wang, Q. Song, Org. Lett., 2021, 23, 4564-4569.

The Suzuki-Miyaura cross-coupling reaction between a diborylmethane derivative and allyl halides or benzyl halides proceeded efficiently in the presence of an appropriate Pd-catalyst at room temperature. The present approach provides functionalized homoallylboronates and alkylboronates with excellent regio- and chemoselectivities.
K. Endo, T. Ohkubo, T. Ishioka, T. Shibata, J. Org. Chem., 2012, 77, 4826-4831.

Allylsilylation allows to install both silyl and allyl groups onto a carbon-carbon double bond directly. Proton-exchanged montmorillonite showed excellent catalytic performances for the allylsilylation of alkenes. Isolation of the reaction intermediate on the montmorillonite surface helped to investigate the reaction mechanism.
K. Motokura, S. Matsunaga, A. Miyaji, Y. Sakamoto, T. Baba, Org. Lett., 2010, 12, 1508-1511.

Enantioselective copper-catalyzed allylic alkylations of Grignard reagents were performed on allylic bromides with a protected hydroxyl or amine functional group using Taniaphos as a ligand. The terminal olefin moiety in the products can be transformed into various functional groups without racemization.
A. W. van Zijl, F. López, A. J. Minnaard, B. L. Feringa, J. Org. Chem., 2007, 72, 2558-2563.

A chemo- and regioselective, Cu-catalyzed asymmetric addition of Grignard reagents to 3-bromopropenyl esters provides allylic esters in high yields and enantioselectivities using Taniaphos as ligand. The method is a practical route to chiral, nonracemic allylic alcohols.
K. Geurts, S. P. Fletcher, B. L. Feringa, J. Am. Chem. Soc., 2006, 128, 15572-15573.

The use of catalytic loadings of picolinaldehyde and Ni(II) salts in catalytic α-allylation of unprotected amino acid esters induces preferential reactivity at the enolizable α-carbon over the free nitrogen with electrophilic palladium π-allyl complexes to produce α-quaternary α-allyl amino acid esters. Additionally, the use of chiral ligands to access enantioenriched α-quaternary amino acid esters from racemic precursors is demonstrated.
P. Fang, M. R. Chaulagian, Z. D. Aron, Org. Lett., 2012, 14, 2130-2133.

Chelated amino acid ester enolates are excellent nucleophiles for allylic alkylations. With these enolates, even terminal π-allyl palladium complexes react without significant isomerization.
K. Krämer, U. Kazmaier, J. Org. Chem., 2006, 71, 8950-8953.

A bis(diisopropylamino)cyclopropenimine-substituted bis-protonated proton sponge can be used as a bifunctional phase-transfer catalyst. The catalyst operates simultaneously as a hydrogen bond donor and a phase-transfer catalyst, facilitating the movement of charged intermediates from the interface to the organic phase.
L. Belding, P. Stoyanov, T. Dudding, J. Org. Chem., 2016, 81, 553-558.

A direct catalytic enantioselective allylation of acyclic α-ketiminoesters provides α-allyl-α-aryl and α-allyl-α-trifluoromethyl amino esters in excellent isolated yield and with high optical purity in the presence of catalytic amounts of indium(I) iodide and commercially available BOX-type ligands. The allylated products are easily converted to enantiomerically enriched α-substituted proline derivatives.
U. Bhakta, P. V. Kattamuri, J. H. Siitonen, L. B. Alemany, L. Kürti, Org. Lett., 2019, 21, 9208-9211.

Efficient Addition of Allylsilanes to α,β-Enones Using Catalytic Indium and Trimethylsilyl Chloride
P. H. Lee, D. Seomoon, S. Kim, K. Nagaiah, S. V. Damle, K. Lee, Synthesis, 2003, 2023-2026.

In a catalytic method for the regioselective allylation of α,β-unsaturated aldehydes, the use of an air-stable diethanolamine-complexed boronic acid (DABO boronate) as the allyl transfer reagent promotes conjugate addition over 1,2-addition. Various aryl- and alkyl-substituted enals provide δ,ε-unsaturated aldehyde products in good yields under mild conditions.
P. C. Roest, N. W. M. Michel, R. A. Batey, J. Org. Chem., 2016, 81, 6774-6778.

In a catalytic method for the regioselective allylation of α,β-unsaturated aldehydes, the use of an air-stable diethanolamine-complexed boronic acid (DABO boronate) as the allyl transfer reagent promotes conjugate addition over 1,2-addition. Various aryl- and alkyl-substituted enals provide δ,ε-unsaturated aldehyde products in good yields under mild conditions.
P. C. Roest, N. W. M. Michel, R. A. Batey, J. Org. Chem., 2016, 81, 6774-6778.

The use of unsaturated methylidene ketones in catalytic conjugate allylations allows a significant expansion in substrate scope and occurs in a highly enantioselective fashion in the presence of a Taddol-derived phosphinite ligand.
L. A. Brozek, J. D. Sieber, J. P. Morken, Org. Lett., 2011, 13, 995-997.

A nickel-catalyzed ring-opening allylation of cyclopropanols with allylic carbonates provides δ,ε-unsaturated ketones in moderate to good yields under mild and neutral conditions. The reaction displays linear selectivity for both linear and branched acyclic allylic carbonates and is also applicable to cyclic allylic carbonates.
Y. Sekiguchi, Y. Y. Lee, N. Yoshikai, Org. Lett., 2021, 23, 5993-5997.

The reaction of alkoxides with boron trichloride results in the generation of cations that can be allylated in subsequent transformations. The absence of Brønsted acids can make a significant difference in such syntheses.
G. W. Kabalka, M.-L. Yao, S. Borella, J. Am. Chem. Soc., 2006, 128, 11320-11321.

G. W. Kabalka, M.-L. Yao, S. Borella, J. Am. Chem. Soc., 2006, 128, 11320-11321.

An Ir-catalyzed enantioselective benzylation reaction of allylic electrophiles can occur directly from aryl acetic acids via stereoselective carbon-carbon bond formation followed by decarboxylation as the terminal event. The absence of a highly basic nucleophile offers broad functional group compatibility that would not be possible employing established protocols.
P. J. Moon, Z. Wei, R. J. Lundgren, J. Am. Chem. Soc., 2018, 140, 17418-17422.

The combination of a halogen bond donor with trimethylsilyl halide is an efficient cocatalytic system for a direct dehydroxylative coupling reaction of alcohol with various nucleophiles, such as allyltrimethylsilane and trimethylcyanide, to give the corresponding adduct in moderate to excellent yields.
M. Saito, N. Tsuji, Y. Kobayashi, Y. Takemoto, Org. Lett., 2015, 17, 3000-3003.

Raising the pKa Limit of "Soft" Nucleophiles in Palladium-Catalyzed Allylic Substitutions: Application of Diarylmethane Pronucleophiles
S.-C. Sha, J. Zhang, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2013, 135, 17602-17609.

Aryl aldehydes couple readily with allylmetals to afford haloallylated products in the presence of boron trihalides. The reactions tolerate a variety of functional groups. Simple aqueous workup of haloallylation reactions, followed by treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene, provides a straightforward route to synthetically useful (E)-1,3-dienes.
M. P. Quinn, M.-L. Yao, G. W. Kabalka, Synthesis, 2011, 3815-3820.

Bifunctional vinylboroate/allylic acetate esters react with Grignard reagents to form tertiary allylic boronates via an 'ate-mediated allylic substitution' (AMAS) approach. The method tolerates a wide range of substrates and Grignard reagents.
B. A. Ondrusek, J. K. Park, D. T. McQuade, Synlett, 2014, 25, 217-220.

Various acetals or alcohols react with allyl(trimethyl)silane or 1-phenyl-2-(trimethylsilyl)acetylene in the presence of a catalytic amount of the Brønsted acid o-benzenedisulfonimide under mild conditions to give good yields of the allylated products. The catalyst can be easily recovered and purified for use in further reactions.
M. Barbero, S. Bazzi, S. Cadamuro, S. Dughera, C. Piccinini, Synthesis, 2010, 315-319.

Allylic gem-dichlorides undergo regio- and enanantioselective copper-catalyzed allylic alkylation with Grignard reagents to afford chiral Z-vinyl chlorides. Subsequent Suzuki cross coupling reactions afford optically active Z-alkenes and 1,3-cis,trans dienes.
M. Giannerini, M. Fañanás-Mastral, B. L. Feringa, J. Am. Chem. Soc., 2012, 134, 4108-4111.

A copper-catalyzed enantioselective defluoroalkylation of linear 1-(trifluoromethyl)alkenes with arylboronate-activated alkyl Grignard reagents provides various gem-difluoroalkenes. Tetraorganoborate complexes generated in situ were the key reactive species for this transformation.
M. Wang, X. Pu, Y. Zhao, P. Wang, Z. Li, C. Zhu, Z. Shi, J. Am. Chem. Soc., 2018, 140, 9061-9065.

An organic photoredox-catalyzed gem-difluoroallylation of α-trifluoromethyl alkenes with alkyl iodides provides gem-difluoroalkene derivatives via C-F bond cleavage. This transition-metal-free transformation utilizes a readily available organic dye (4CzIPN) as the sole photocatalyst and N,N,N',N'-tetramethylethylenediamine as the radical activator.
S. Yan, W. Yu, J. Zhang, H. Fan, Z. Lu, Z. Zhang, T. Wang, J. Org. Chem., 2022, 87, 1574-1584.

An efficient photoredox catalytic radical addition/defluoroalkylation coupling reaction between derivatives of primary amines and trifluoromethyl-substituted alkenes provides a series of gem-difluoroalkenes under visible light irradiation. This reaction offers a broad substrate scope and good functional group tolerance.
B. Wang, C.-T. Wang, X.-S. Li, X.-Y. Liu, Y.-M. Liang, Org. Lett., 2022, 24, 6566-6570.

An efficient photoredox catalytic radical addition/defluoroalkylation coupling reaction between derivatives of primary amines and trifluoromethyl-substituted alkenes provides a series of gem-difluoroalkenes under visible light irradiation. This reaction offers a broad substrate scope and good functional group tolerance.
B. Wang, C.-T. Wang, X.-S. Li, X.-Y. Liu, Y.-M. Liang, Org. Lett., 2022, 24, 6566-6570.

Zn mediates a decarboxylative/defluorinative alkylation of α-trifluoromethyl alkenes with N-hydroxyphthalimide esters as radical precursors. Several α-trifluoromethyl alkenes were readily coupled to a wide range of primary, secondary, and tertiary radicals, affording the desired gem-difluoroethylenes in good yields.
H.-W. Du, Y. Chen, J. Sun, Q.-S. Gao, H. Wang, M.-D. Zhou, Org. Lett., 2020, 22, 9342-9345.

In the “deacylative allylation”, the coupling partners, ketone pronucleophiles and readily available allylic alcohols undergo in situ retro-Claisen activation to generate an allylic acetate and a carbanion. In the presence of palladium, these reactive intermediates undergo catalytic coupling to form a new C-C bond.
A. J. Grenning, J. A. Tunge, J. Am. Chem. Soc., 2011, 133, 14785-14794.

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.

α-Cyano aldehydes undergo selective transition-metal-catalyzed allylation to provide α-allylated nitriles. The transformation leads to linear allylated nitriles with palladium catalysts whereas an iridium catalyst provides branched substitution products. TBD-catalyzed retro-Claisen cleavage is leveraged to attain selective monoallylation.
T. Maji, J. A. Tung, Org. Lett., 2014, 16, 5072-5075.

Pd-catalyzed asymmetric allylic alkylation of nitroalkanes and monosubstituted allylic substrates affords products with two adjacent chiral centers in excellent regio-, diastereo-, and enantioselectivities. Products can be transformed to optically active homoallylamines, 2,3-disubstituted tetrahydropyridines, and α,β-disubstituted amino acid derivatives.
X.-F. Yang, W.-H. Yu, C.-H. Ding, Q.-P. Ding, S.-L. Wan, X.-L. Hou, L.-X. Dai, P.-J. Wang, J. Org. Chem., 2013, 78, 6503-6509.

Allyl nitroacetates undergo decarboxylative allylation to provide tertiary nitroalkanes in high yield within several minutes under ambient conditions. The preparation of substrate allyl nitroacetates by tandem Knoevenagel/Diels-Alder sequences allows the facile synthesis of relatively complex substrates that undergo diastereoselective decarboxylative allylation.
A. J. Grenning, J.A. Tunge, Org. Lett., 2010, 12, 740-742.

A copper-catalyzed regio- and enantioselective hydroallylation of alkenyl boronates and boramides with allylic phosphates in the presence of hydrosilanes enables an efficient synthesis of a broad range of homoallylic alkylboron compounds in good yields and with high enantioselectivities.
J. T. Han, W. J. Jang, N. Kim, J. Yun, J. Am. Chem. Soc., 2016, 138, 15146-15149.

The combination of copper(I) bromide and H8-BINOL derived phosphoramidite ligand catalyzes an enatiotopic-group-selective allylation of gem-diborylalkanes with allyl bromides to provide enantioenriched homoallylic boronate esters in good yields with high enantiomeric ratios under mild conditions.
M. Kim, B. Park, M. Shin, S. Kim, J. Kim, M.-H. Baik, S. H. Cho, J. Am. Chem. Soc., 2021, 143, 1069-1077.

In the presence of IMes-Cu catalyst, a tandem hydrocupration/allylation of alkenyl boronates with allyl phosphate efficiently proceeds in the presence of a hydrosilane via in situ generated Β-α-copper intermediates. Mono- and disubstituted alkenyl boronates were effective in the reaction with terminal allyl phosphates, but trisubstituted substrates showed limited reactivity.
W. J. Jang, J. T. Han, J. Yun, Synthesis, 2017, 49, 4753-4758.

In a Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes, differently substituted gem-diborylalkanes and allylic electrophiles can be employed, and various synthetic valuable functional groups are tolerated. The use of chiral N-heterocyclic carbene (NHC) ligands enables an asymmetric version.
Z.-Q. Zhang, B. Zhang, X. Lu, J.-H. Liu, X.-Y. Lu, B. Xiao, Y. Fu, Org. Lett., 2016, 18, 952-955.

An iridium-catalyzed enantioconvergent coupling of the versatile boron-stabilized organozinc reagent BpinCH2ZnI with racemic branched allylic carbonates provides various chiral homoallylic organoboronic esters in good yields with excellent enantioselectivities. The homoallylboronates can easily be converted to other useful families of compounds.
P. Guo, M. Zhan, J. Org. Chem., 2021, 86, 9905-9913.

A modular, practical, and general palladium-catalyzed, radical three-component coupling enables selective 1,4-difunctionalization of unactivated 1,3-dienes, such as butadiene, by employing different commercially available nitrogen-, oxygen-, sulfur-, or carbon-based nucleophiles and unactivated alkyl bromides.
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Asymmetric allylic substitution with organolithium reagents enables a highly regio- and enantioselective desymmetrization of meso-1,4-dibromocycloalk-2-enes to afford enantioenriched bromocycloalkenes. The cycloheptene products undergo an unusual ring contraction.
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Enantioselective Allylic Carbon-Carbon Bond Construction