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Article title

Asymmetric Pd-catalyzed allylic substitution using a large sugar-based monophosphite ligand library. Scope and limitations.


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We have applied a modular sugar-based
phosphite ligand library for the Pd-catalyzed allylic
substitution reactions of several substrates. These ligands
are derived from D-(+)-glucose, D-(+)-galactose and D-(+)-
fructose, which lead to a wide range of sugar backbones,
and contain several substituents at the C-3 carbon of
the furanoside backbone and several substituents/
configurations in the biaryl moiety, with different steric
and electronic properties. Systematic variation of the
ligand parameters indicates that the catalytic performance
(activities and enantioselectivities) is highly affected by
sugar backbone, the substituents at the C-3 carbon of
the furanoside backbone, the configurations at the C-3
and C-4 carbons of the ligand backbone and the type
of substituents/configurations in the biaryl phosphite
moiety as well as the substrate type. For disubstituted
substrates moderate enantioselectivities (up to 72%) were
achieved using ligand L8d, while for monosubstituted
substrates the highest enantioselectivities (up to 40%)
were obtained using ligand L9a.







Physical description


10 - 8 - 2014
12 - 3 - 2014
3 - 3 - 2014


  • Departament de Química Física i Inorgànica. Universitat
    Rovira i Virgili. C/ Marcelli Domingo, s/n. 43007 Tarragona,
  • Institute of Chemical Research of Catalonia (ICIQ), Av.
    Països Catalans 16, 43007, Tarragona, Spain
  • Departament de Química Física i Inorgànica. Universitat
    Rovira i Virgili. C/ Marcelli Domingo, s/n. 43007 Tarragona,
  • Departament de Química Física i Inorgànica. Universitat
    Rovira i Virgili. C/ Marcelli Domingo, s/n. 43007 Tarragona,


  • [1] Tsuji, J., Palladium reagents and catalysis, innovations inorganic synthesis, Wiley, New York, 1995.
  • [2] Trost, B.M., van Vranken, D.L., Asymmetric transition metalcatalyzedallylic alkylations, Chem. Rev., 1996, 96, 395-422.
  • [3] Pfaltz, A., Lautens, M., In: Jacobsen, E.N., Pfaltz, A., Yamamoto,H. (Eds.), Comprehensive asymmetric catalysis, Springer-Verlag: Berlin, 1999, Vol. 2, Chapter 24.
  • [4] Helmchen, G., Pfaltz, A., Phosphinooxazolines: a new class ofversatile, modular P,N-ligands for asymmetric catalysis, Acc.Chem. Res., 2000, 33, 336-345.
  • [5] Masdeu-Bultó, A.M., Diéguez, M., Martin, E., Gómez, M., Chiralthioether ligands: coordination chemistry and asymmetriccatalysis, Coord. Chem. Rev., 2003, 242, 159-201.
  • [6] Trost, B.M., Crawley, M.L., Asymmetric transition-metalcatalyzedallylic alkylations: applications in total synthesis,Chem. Rev., 2003, 103, 2921-2944.
  • [7] Martin, E., Diéguez, M.C.R., Thioether containing ligands forasymmetric allylic substitution reactions, C. R. Chemie, 2007,10, 188-205.
  • [8] Lu, Z., Ma, S., Metal-Catalyzed Enantioselective allylationin asymmetric synthesis, Angew. Chem. Int. Ed., 2008, 47,258-297.
  • [9] Diéguez, M., Pàmies, O., Biaryl phosphites: new efficientadaptative ligands for Pd-catalyzed asymmetric allylicsubstitution reactions, Acc. Chem. Res., 2010, 43, 312-322.
  • [10] van Leeuwen, P.W.N.M., Kramer, P.C.J., Claver, C., Pàmies,O., Diéguez, M. Phosphite-containing ligands for asymmetriccatalysis, Chem. Rev., 2011, 111, 2077-2118.
  • [11] Guerrero Rios, I., Rosas-Hernandez, A., Martin, E., Recentadvances in the application of chiral phosphine ligands inPd-catalysed asymmetric allylic alkylation, Molecules, 2011, 16,970-1010.[Crossref]
  • [12] Arseniyadis, S., Fournier, J., Thangavelu, S., Lozano, O.,Prevost, S., Archambeau, A., Menozzi, C., Cossy, J., Palladiumcatalyzedallylic alkylation of allyl dienol carbonates: reactivity,regioselectivity, enantioselectivity, and synthetic applications,Synlett, 2013, 24, 2350-2364.[Crossref]
  • [13] Yan, Y.-Y., RajanBabu, T.V., Ligand tuning in asymmetriccatalysis: mono- and bis-phospholanes for a prototypicalPd-catalyzed asymmetric allylation reaction, Org. Lett., 2000,2, 199-202.
  • [14] Zhang, X., WO Patent 03/040149 A2, 2003.
  • [15] Mikhel, I.S., Bernardinelli, G., Alexakis, A., Chiralp-monodentate phosphoramidite and phosphite ligands for theenantioselective Pd-catalyzed allylic alkylation, Inorg. Chim.Acta, 2006, 359, 1826-1836.
  • [16] Gavrilov, K.N., Tsarev, V.N., Lyubimov, S.E., Shiryaev, A.A.,Zhelov, S.V., Bondarev, O.G., Davankov, V.A., Kabro, A.A.,Moiseev, S.K., Kalinin, V.N., Chiral P*-monodentate phosphiteligand for Pd-catalysed asymmetric allylation reactions,Mendeleev Commun., 2003, 134-136.[Crossref]
  • [17] Tsarev, V.N., Lyubimov, S.E., Shiryaev, A.A., Zheglov, S.V.,Bondarev, O.G., Davankov, V.A., Kabro, A.A., Moiseev, S.K.,Kalinin, V.N., Gavrilov, K.N., P-chiral monodentate diamidophosphites-new and efficient ligands for palladium-catalysedasymmetric allylic substitution, Eur. J. Org. Chem., 2004,2214-2222.[Crossref]
  • [18] Gavrilov, K.N., Lyubimov, S.E., Petrovskii, P.V., Zheglov, S.V.,Safranov, A.S., Skazov, R.S., Davankov, V.A., Facile one-potsynthesis of BINOL- and H8-BINOL-based aryl phosphitesand their use in palladium catalysed asymmetric allylation,Tetrahedron, 2005, 61, 10514-10520.
  • [19] Gavrilov, K.N., Lyubimov, S.E., Zheglov, S.V., Benetsky, E.B.,Davankov, V.A., Enantioselective Pd-catalysed allylation withBINOL-derived monodentate phosphite and phosphoramiditeligands, J. Mol. Catal. A: Chem., 2005, 231, 255-260.
  • [20] Gavrilov, K.N., Lyubimov, S.E., Zheglov, S.V., Benetsky, E.B.,Petrovskii, P.V., Rastorguev, E.A., Grishina, T.B., Davankov, V.A.,MOP-type binaphthyl phosphite and diamidophosphite ligandsand their application in catalytic asymmetric transformations,Adv. Synth. Catal., 2007, 349, 1085-1094.
  • [21] Gavrilov, K.N., Lyubimov, S.E., Bondarev, O.G., Marksimova,M.G., Zheglov, S.V., Petrovskii, P.V., Davankov, V.A., Reetz, M.T.,Chiral ionic phosphites and diamidophosphites: a novel groupof efficient ligands for asymmetric catalysis, Adv. Synth. Catal.,2007, 349, 609-616.
  • [22] Prétôt, R., Pfaltz, A., New ligands for regio- and enantiocontrolin Pd-catalyzed allylic alkylations, Angew. Chem. Int. Ed., 1998,37, 323-325.
  • [23] Diéguez, M., Jansat, S., Gomez, M., Ruiz, A., Muller, G.,Claver, C., Diphosphites as a promising new class of ligands inPd-catalysed asymmetric allylic alkylation, Chem. Commun.,2001, 1132-1133.
  • [24] Pàmies, O., Diéguez, M., Claver, C., New Phosphite-oxazolineligands for efficient Pd-catalyzed substitution reactions, J. Am.Chem. Soc., 2005, 127, 3646-3647.
  • [25] Mata, Y., Diéguez, M., Pàmies, O., Claver, C., Newcarbohydrate-based phosphite-oxazoline ligands as highlyversatile ligands for palladium-catalyzed allylic substitutionreactions, Adv. Synth. Catal., 2005, 347, 1943-1947.
  • [26] Diéguez, M., Pàmies, O., Claver, C., Modular furanosidediphosphite ligands for Pd-catalyzed asymmetric allylicsubstitution reactions: scope and limitations, Adv. Synth.Catal., 2005, 347, 1257-1266.
  • [27] Pàmies, O., Diéguez, M., Screening of a phosphite-phosphoramiditeligand library for palladium-catalysed asymmetricallylic substitution reactions: the origin of enantioselectivity,Chem. Eur. J., 2008, 14, 944-960.[Crossref]
  • [28] Diéguez, M., Pàmies, O., Modular phosphite-oxazoline/oxazineligand library for asymmetric Pd-catalyzed allylic substitutionreactions: scope and limitations-origin of enantioselectivity,Chem. Eur. J., 2008, 14, 3653-3669.[Crossref]
  • [29] Mata, Y., Pàmies, O., Diéguez, M., pyranoside phosphiteoxazolineligand library: highly efficient modular P,N ligandsfor palladium-catalyzed allylic substitution reactions. A studyof the key palladium allyl intermediates, Adv. Synth. Catal.,2009, 351, 3217-3234.
  • [30] Raluy, E., Pàmies, O., Diéguez, M., Modular furanosidephosphite-phosphoroamidites, a readily available ligandlibrary for asymmetric palladium-catalyzed allylic substitutionreactions. Origin of enantioselectivity, Adv. Synth. Catal., 2009,351, 1648-1670.
  • [31] Mazuela, J., Pàmies, O., Diéguez, M., A new modularphosphite-pyridine ligand library for asymmetric Pd-catalyzedallylic substitution reactions: a study of the key Pd-π-allylintermediates, Chem. Eur. J., 2013, 19, 2416-2432.[Crossref]
  • [32] Mazuela, J., Pàmies, O., Diéguez, M., Phosphite-thiazolineversus phosphite-oxazoline for Pd-catalyzed allylic substitutionreactions: a case for comparison, ChemCatChem, 2013, 5,1504-1516.
  • [33] Diéguez, M., Pàmies, O., Claver, C., Ligands derived fromcarbohydrates for asymmetric catalysis, Chem. Rev., 2004, 104,3189-3216.
  • [34] Diéguez, M., Pàmies, O., Ruiz, A., Díaz, Y., Castillón, S., Claver,C., Carbohydrate derivative ligands in asymmetric catalysis,Coord. Chem. Rev., 2004, 248, 2165-2192.
  • [35] Diéguez, M., Ruiz, A., Claver, C., Tunable furanosidediphosphite ligands. A powerful approach in asymmetriccatalysis, Dalton Trans., 2003, 2957-2963.
  • [36] Diéguez, M., Pàmies, O., Ruiz, A., Claver, C., In: Malhotra,S.V. (Ed.), Methodologies in asymmetric catalysis, AmericanChemical Society, Washington DC, 2004.
  • [37] Diéguez, M., Pàmies, O., Claver, C., Recent advances inRh-catalyzed asymmetric hydroformylation using phosphiteligands, Tetrahedron: Asymmetry, 2004, 15, 2113-2122.[Crossref]
  • [38] Diéguez, M., Claver, C., Pàmies, O., Recent progress inasymmetric catalysis using chiral carbohydrate-based ligands,Eur. J. Org. Chem., 2007, 4621-4634.[Crossref]
  • [39] Woodward, S., Diéguez, M., Pàmies, O., Use of sugar-basedligands in selective catalysis: recent developments, Coord.Chem. Rev., 2010, 254, 2007-2030.
  • [40] Boysen, M.M.K., Carbohydrates as synthetic tools in organicchemistry, Chem. Eur. J., 2007, 13, 8648-8659.[Crossref]
  • [41] Benessere, V., Del Litto, R., De Roma, A., Ruffo, F.,Carbohydrates as building blocks of privileged ligands, Coord.Chem. Rev., 2010, 254, 390-401.
  • [42] Boysen, M.M.K., Carbohydrates: tools for stereoselectivesynthesis, Wiley-VCH, Weinheim, 2013.
  • [43] Reetz, M.T., Mehler, G., Highly enantioselective Rh-catalyzedhydrogenation reactions based on chiral monophosphiteligands, Angew. Chem. Int. Ed., 2000, 39, 3889-3890.
  • [44] Reetz, M.T., Goossen, L.J., Meiswinkel, A., Paetzold, J., Jensen,J.F., Enantioselective Rh-catalyzed hydrogenation of vinylcarboxylates with monodentate phosphite ligands, Org. Lett.,2003, 5, 3099-3101.
  • [45] Huang, H., Zheng, Z., Luo, H., Bai, C., Hu, X., Chen, H., Chiralmonophosphites derived from carbohydrate: conformationaleffect in catalytic asymmetric hydrogenation, Org. Lett., 2003,5, 4137-4139.
  • [46] Huang, H., Liu, X., Chen, S., Chen, H., Zheng, Z., Carbohydratederivedmonophosphite ligands for Rh-catalyzedenantioselective hydrogenation of α- and β-dehydroamino acidesters, Tetrahedron: Asymmetry, 2004, 15, 2011-2019.[Crossref]
  • [47] Huang, H., Liu, X., Chen, H., Zheng, Z., Monophosphite ligandsderived from carbohydrates and H8-BINOL: highly enantioselectiveRh-catalyzed asymmetric hydrogenations, Tetrahedron:Asymmetry, 2005, 16, 693-697.[Crossref]
  • [48] Alegre, S., Alberico, E., Pàmies, O., Diéguez, M., Rh-catalyzedasymmetric hydrogenation using a furanoside monophosphitesecond-generation ligand library: scope and limitations,Tetrahedron: Asymmetry, 2014, 25, 258-262.[Crossref]
  • [49] You, S.-L., Zhu, X.-Z., Luo, Y.-M., Hou, X.-L., Dai, L.-X., Highlyregio- and enantioselective Pd-catalyzed allylic alkylationand amination of monosubstituted allylic acetates with novelferrocene P,N-ligands, J. Am. Chem. Soc., 2001, 123, 7471-7472.
  • [50] Hilgraf, R., Pfaltz, A., Chiral bis(N-tosylamino)phosphineandTaddol-phosphite-oxazolines as ligands in asymmetriccatalysis, Synlett, 1999, 1814-1816.[Crossref]
  • [51] This contrasts with the preferential formation of the linearisomer 5 observed using tartrate-based monophosphoroamiditeligands, see ref. 15.
  • [52] Suárez, A., Pizzano, A., Fernández, I., Khiar, N., Monodentatephosphites with carbohydrate substituents and theirapplication in rhodium catalysed asymmetric hydrosilylationreactions, Tetrahedron: Asymmetry, 2001, 12, 633-642.[Crossref]
  • [53] Mata, Y., Diéguez, M., Pàmies, O., Woodward, S., screeningof a modular sugar-based phosphite ligand library in theasymmetric nickel-catalyzed trialkylaluminum addition toaldehydes, J. Org. Chem., 2006, 71, 8159-8165.
  • [54] Alegre, S., Diéguez, M., Pàmies, O., Sugar-monophosphiteligands applied to the asymmetric Ni-catalyzed trialkylaluminumaddition to aldehydes, Tetrahedron: Asymmetry,2011, 22, 834-839.[Crossref]
  • [55] Auburn, P.R., Mackenzie, P.B., Bosnich B., Asymmetricsynthesis. Asymmetric catalytic allylation using palladiumchiral phosphine complexes, J. Am. Chem. Soc., 1985, 107,2033-2046.
  • [56] Jia, C., Müller, P., Mimoun, H., Palladium-catalyzed allylicacetoxylation of olefins using hydrogen peroxide as oxidant, J.Mol. Cat. A: Chem., 1995, 101, 127-136.
  • [57] Lehman, J., Lloyd-Jones, G.C., Regiocontrol and stereoselectivityin tungsten-bipyridine catalysed allylic alkylation,Tetrahedron, 1995, 51, 8863-8874.
  • [58] Pàmies, O., van Strijdonck, G.P.F., Diéguez, M., Deerenberg,S., Net, G., Ruiz, A., Claver, C., Kamer, P.C.J., van Leeuwen,P.W.N.M., Modular furanoside phosphite ligands forasymmetric Pd-catalyzed allylic substitution, J. Org. Chem.,2001, 66, 8867-8871.
  • [59] Evans, D.A., Campos, K.R., Tedrow, J.R., Michael, F.E., Gagné,M.R., Application of chiral mixed phosphorus/sulfur ligands topalladium-catalyzed allylic substitutions, J. Am. Chem. Soc.,2000, 122, 7905-7920.
  • [60] Pericàs, M.A., Puigjaner, C., Riera, A., Vidal-Ferran, A.,Gómez, M., Jiménez, F., Muller, G., Rocamora, M., Modularbis(oxazoline) ligands for palladium catalyzed allylic alkylation:unprecedented conformational behaviour of a bis(oxazoline)palladium η3-1,3-diphenylallyl complex, Chem. Eur. J., 2002, 8,4164-4178.
  • [61] Janssen, J.P., Helmchen, G., First enantioselective alkylationsof monosubstituted allylic acetates catalyzed by chiral iridiumcomplexes, Tetrahedron Lett., 1997, 38, 8025-8026.

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