Allylic Substitution, Allylation
The cross-coupling reaction of aryl and vinyl boronic acids and allylic alcohols proceeded smoothly in toluene or dioxane in the presence of a (triphenyl phosphite)palladium catalyst to give the corresponding allylbenzene derivatives and 1,4-dienes. Neither cocatalysts for promoting C-O bond cleavage of allylic alcohols nor bases for activation of organoboron reagents are required.
Y. Kayaki, T. Koda, T. Ikariya, Eur. J. Org. Chem., 2004, 4989-4993.
Palladium-catalyzed allyl cross-coupling reaction of allylic acetates with various boronic acids gave allyl arene derivatives in good yields at room temperature in the presence of a catalytic amount of Pd(OAc)2 with phosphine-free hydrazone as ligand.
T. Mino, K. Kajiwara, Y. Shirae, M. Sakamoto, T. Fujita, Synlett, 2008, 2711-2715.
Tributylmagnesate (nBu3MgLi) and the more reactive dibutylisopropylmagnesate (iPrnBu2MgLi) induce facile iodine/bromine-magnesium exchange to provide various polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using this method proceeds with retention of configuration of the double bond.
A. Inoue, K. Kitagawa, H. Shinokubo, K. Oshima, J. Org. Chem., 2001, 66, 4333-4339.
A protocol with small amounts of palladium and ligand, without any additive solvent and under microwave heating enables cross-coupling reactions between 2-methyl-2-propen-1-ol and various boronic acids to yield aromatic 2-methylallyl derivatives.
C. Tabélé, C. Curti, N. Primas, Y. Kabri, V. Remusat, P. Vanelle, Synthesis, 2015, 47, 3339-3346.
A cross-coupling reaction between aryl- and vinylboronic acids and various allylic bromides proceeded without the use of a transition-metal catalyst to give the corresponding allylated products in good yields. The use of an inorganic base and a small amount of water is crucial in obtaining good performance in the present transition-metal-free reaction.
M. Ueda, K. Nishimura, R. Kashima, I. Ryu, Synlett, 2012, 23, 1085-1089.
The cross-coupling reactions of allylboronic acid pinacol ester derivatives with aryl and heteroaryl halides occurred with high selectivity at the α-carbon of the allylboron reagent in the presence of Pd-PEPPSI-IPent precatalyst and aqueous KOH in refluxing THF. In the case of trisubstituted allylboronates with different substituents on the olefin, minor olefin geometry isomerization was observed.
J. L. Farmer, H. N. Hunter, M. G. Organ, J. Am. Chem. Soc., 2012, 134, 17470-17473.
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.
A copper-catalyzed SN2'-selective arylation of various allylic chlorides with arylboronic esters in the presence of a wide range of functional groups leads to branched products in high yield. A mechanism is proposed on the basis of the results of stoichiometric experiments and the isolation of the proposed intermediate.
A. M. Whittaker, R. P. Rucker, G. Lalic, Org. Lett., 2010, 12, 3216-3218.
Allyl-aryl coupling between allylic acetates and arylboronic acids took place in the presence of catalytic amounts of Pd(OAc)2, 1,10-phenanthroline, and AgSbF6 with high γ-selectivity and E:Z-selectivity. The reaction of an optically active allylic acetate with an α-stereogenic center proceeded with excellent α-to-γ chirality transfer.
H. Ohmiya, Y. Makida, T. Tanaka, M. Sawamura, J. Am. Chem. Soc., 2008, 130, 17276-17277.
In situ generated palladium(0) nanoparticles catalyze an efficient cross-coupling of allyl acetates with aryl and vinyl siloxanes. The reactions are stereoselective, and linear (E)-coupling products are obtained both from cis and trans allyl acetates. The coupling with vinyl siloxanes provides a novel protocol for the synthesis of 1,4-pentadienes.
R. Dey, K. Chattopadhyay, B. C. Ranu, J. Org. Chem., 2008, 73, 9461-9464.
A room-temperature Ni-catalyzed reductive coupling of aryl bromides with secondary alkyl bromides provides products in good to excellent yields. Slight modification of this protocol allows efficient coupling of activated aryl chlorides with cyclohexyl bromide and aryl bromides with allylic acetate.
S. Wang, Q. Qian, H. Gong, Org. Lett., 2012, 14, 3352-3355.
An efficient Hiyama coupling reaction between benzylic halides and aryltrialkoxysilanes using Pd nanoparticles allows the synthesis of a diverse range of diarylmethanes which are ubiquitous units of natural products and pharmaceuticals.
D. Srimani, A. Bej, A. Sarkar, J. Org. Chem., 2010, 75, 4296-4299.
Coupling of sterically hindered aryl and activated alkyl chlorides bearing β-hydrogens has been successfully achieved by using N-heterocyclic carbene (NHC)Pd-carboxylate complexes as catalysts.
R. Singh, M. S. Viciu, N. Kramareva, O. Navarro, S. P. Nolan, Org. Lett., 2005, 7, 1829-1832.
In situ generated allylindium reagents could be effectively cross-coupled with aryl halides. The best results were obtained with catalytic amounts of Pd2dba3CHCl3 and Ph3P in the presence of 3 equiv of LiCl in DMF at 100 °C.
P. H. Lee, S.-y. Sung, K. Lee, Org. Lett., 2001, 3, 3201-3204.
A γ-selective, palladium-catalyzed cross-coupling of sodium (Z)-2-butenyldiethylsilanolate provides high yields and site selectivity with electron-rich, electron-poor, sterically hindered, and heteroaromatic bromides. The use of a configurationally homogeneous (Z)-silanolate, nontransferable ethyl groups, and a sterically bulky trialkylphosphonium tetrafluoroborate salt are critical to the success of the method.
S. E. Denmark, N. S. Werner, Org. Lett., 2011, 13, 4596-4599.
A nickel-catalyzed hydroarylation of secondary homoallyl carbonates with arylboronic acids provides an efficient access to a broad range of hydroarylation products in high yields with high functional group compatibility without the use of an external hydride source.
T. Hamaguchi, Y. Takahashi, H. Tsuji, M. Kawatura, Org. Lett., 2020, 22, 11241129.
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.
Functionalized diarylzinc reagents react readily with allylic chlorides or phosphates in the presence of Co(acac)2 as catalyst to give the SN2 products in high yields and with retention of the double-bond configuration. Functionalities such as ester, ketone, or cyano are tolerated.
G. Dunet, P. Knochel, Synlett, 2007, 1383-1386.
The use of Zn powder in the presence of LiCl in THF allows a simple, high-yielding preparation of a broad range of functionalized aryl- and heteroarylzinc reagents. The synthesis of alkylzinc reagents was performed from inexpensive alkyl bromides.
A. Krasovski, V. Malakhov, A. Gavryushin, P. Knochel, Angew. Chem. Int. Ed., 2006, 45, 6040-6044.
The success of a regioselective and enantiospecific, nickel-catalyzed cross-coupling of unsymmetric 1,3-disubstituted allylic pivalates with arylboroxines relies on the use of BnPPh2 as a supporting ligand and NaOMe as a base. This method shows excellent functional group tolerance and broad scope in both the allylic pivalate and arylboroxine, enabling the preparation of 1,3-diaryl allylic products in high yields.
H. D. Srinivas, Q. Zhou, M. P. Watson, Org. Lett., 2014, 16, 3596-3599.
Generation of a π-allyl Pd species directly from a 1,3-diene via a Pd-catalyzed aerobic alcohol oxidation enables a palladium-catalyzed reductive cross-coupling of 1,3-dienes with boronic esters. Both the scope of the process and the origin of a highly selective 1,2-addition are discussed.
L. Liao, M. S. Sigman, J. Am. Chem. Soc., 2010, 132, 10209-10211.
A copper-catalyzed asymmetric allylic substitution of γ,γ-disubstituted allyl phosphates with arylboronates for the construction of quaternary stereocenters achieves high regio- and enantioselectivities by employing a hydroxy-bearing chiral N-heterocyclic carbene ligand. Both E and Z substrates provide the same enantiomer as the major product.
M. Takeda, K. Takatsu, R. Shintani, T. Hayashi, J. Org. Chem., 2014, 79, 2354-2367.
The Suzuki-Miyaura cross-coupling with chiral γ,γ-disubstituted allylboronates provides nonracemic compounds with quaternary centers with high regioselectivity and enantiospecificity in the presence of RuPhos ligand. The reaction occurs by transmetalation with allyl migration, followed by rapid reductive elimination.
B. Potter, E. K. Edelstein, J. P. Morken, Org. Lett., 2016, 18, 3286-3289.
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.
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 Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl acetates, aldehydes, and organoboranes provides (Z)-anti-homoallylic alcohols with high levels of diastereoselectivity and alkene stereocontrol.
Y. Horino, A. Aimono, H. Abe, Org. Lett., 2015, 17, 2824-2827.
Palladium-catalyzed coupling reactions of functionalized allylboronic acids with various iodobenzenes under standard Suzuki-Miyaura coupling conditions afforded selectively the branched allylic products in high to excellent yields.
S. Sebelius, V. J. Olsson, O. A. Wallner, K J. Szabó, J. Am. Chem. Soc., 2006, 128, 8150-8151.
Sodium allyldimethylsilanolates and 2-butenyldimethylsilanolates undergo cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. Reactions of allyldimethylsilanolate take place in DME with allylpalladium chloride dimer whereas 2-butenyldimethylsilanolate delivered branched products in toluene in the presence of Pd(dba)2 and norbornadiene as ligand.
S. E. Denmark, N. S. Werner, J. Am. Chem. Soc., 2008, 130, 16382-16393.
An efficient palladium-catalyzed Suzuki-Miyaura reaction of oxygen atom-substituted allylboronates with aryl/vinyl bromides, iodides, and triflates provides various allylic siloxanes with high efficiency and excellent regioselectivity. This alternative approach for the synthesis of allylic alcohols offers broad substrate scope, excellent functional group tolerance, and gram-scale preparation.
J. Li, X. Zhang, Y. Yao, Y. Gao, W. Yang, W. Zhao, J. Org. Chem., 2022, 87, 6951-6959.
A Pd-catalyzed gem-difluoroallylation of organoborons using 3-bromo-3,3-difluoropropene (BDFP) proceeds in high efficiency with high α/γ-substitution regioselectivity. The reaction offers low catalyst loading (0.8 to 0.01 mol %), broad substrate scope, and excellent functional group compatibility, thus providing a facile route for practical application in drug discovery and development.
Q.-Q. Min, Z. Yin, Z. Feng, W.-H. Guo, X. Zhang, J. Am. Chem. Soc., 2014, 136, 1230-1233.
Silylated cyanohydrins of iodo-substituted aryl, heteroaryl, or cycloalkenyl ketones undergo an I/Mg-exchange using i-PrMgCl·LiCl. After subsequent reactions with electrophiles, a facile deprotection produces polyfunctional ketones in good overall yiels. An extension to aromatic iodoaldehydes is described.
C.-Y. Liu, H. Ren, P. Knochel, Org. Lett., 2006, 8, 617-629.
Treatment of fluorapatite with an aqueous solution of RhCl3 resulted in rhodium-exchanged fluorapatite catalyst (RhFAP), which successfully promoted cross coupling of Baylis-Hillman adducts with a variety of arylboronic acids to yield trisubstituted olefins in a highly stereoselective manner. RhFAP was recovered quantitatively by simple filtration and reused with almost consistent activity.
M. L. Kantam, K. B. S. Kumar, B. Sreedhar, J. Org. Chem., 2008, 73, 320-322.
A nickel-catalyzed cross-coupling of allylic alkyl ethers with organoboron compounds provides the corresponding products in very good yields via the cleavage of the inert C(sp3)-O(alkyl) bonds with wide functional group tolerance and excellent regioselectivity. A gram-scale reaction and late-stage modification of biologically active compounds further prove the practicality of this method.
X. Li, Y. Li, Z. Zhang, X. Shi, R. Liu, Z. Wang, X. Li, D. Shi, Org. Lett., 2021, 23, 6612-6616.
A regioselective oxidative allylic C(sp3)-H arylation of readily available unactivated terminal and internal olefins with a broad range of heteroaryl boronic acids is catalyzed by cheap, abundant, and nontoxic Cu2O. This method does not require traditional coupling partners with preinstalled leaving groups at the allylic position, thus offering an alternative method to allylic arylation.
S. Pal, M. Cotard, B. Gérardin, C. Hoarau, C. Schneider, Org. Lett., 2021, 23, 3130-3135.
Palladium-catalyzed cross-coupling of hypervalent arylsiloxane derivatives with allylic benzoates proceeded in very good yields. Arylation occurred with complete inversion of configuration. The scope and limitations of this reaction is summarized.
R. Correia, P. DeShong, J. Org. Chem., 2001, 66, 7159-7165.
A highly enantioselective Rh-catalyzed asymmetric allylic substitution allows the desymmetrization of meso cyclopent-2-ene-1,4-diethyl dicarbonates. Depending on the ligand, each of two regioisomeric products can be obtained in good yield and excellent enantioselectivity. Whereas bisphosphine P-Phos ligands form trans-1,2-arylcyclopentenols, Segphos ligands lead predominantly to trans-1,4-arylcyclopentenols.
F. Menard, D. Perez, D. S. Roman, T. M. Chapman, M. Lautens, J. Org. Chem., 2010, 75, 4056-4068.