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Selectivity in Palladium-Catalyzed Allylic Substitution

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Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 38))

Abstract

The present chapter introduces the basic fundaments of the palladium-catalyzed allylic substitution reaction. After a brief introduction, the reaction is explored into the different steps of the catalytic cycle in a chronological order. Formation of the crucial η 3-allyl palladium complexes is first commented, followed by a brief description of the static isomerism and dynamic features related to these compounds. Synthetic opportunities to intercept these complexes are then presented. Selectivity is then addressed with a first focus on regioselectivity and memory effects. Finally, selected examples of enantioselective versions are presented and classified according to the position of the enantiodiscriminating step in the catalytic cycle.

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Notes

  1. 1.

    Throughout this chapter, brackets around palladium atom in the notation of a generic (charged or neutral) allyl complex intend to render implicit the dative ligands. An asterisk next to the brackets indicates the presence of a chiral (usually enantiopure) ligand.

  2. 2.

    As we will see later, this π-allyl palladium(II) complex can be also generated via interaction between an alkene and a PdX2 complex.

  3. 3.

    Metal-catalyzed allylic alkylation to afford branched products can be obtained using transition metals other than palladium. However, this topic is beyond the scope of the present chapter.

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Acknowledgments

The authors warmly thank Professors Francesco Sannicolò and Guy Lloyd-Jones for stimulating discussions.

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Authors and Affiliations

  1. UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, FR2769, Case 183, F-75252, Paris Cedex 05, France

    Giovanni Poli, Guillaume Prestat & Frédéric Liron

  2. Lehrstuhl für Organische Chemie I, Technische Universität München, Lichtenbergstr. 4, 85747, Garching, Germany

    Claire Kammerer-Pentier

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  1. Giovanni Poli
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Correspondence to Giovanni Poli .

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  1. Inst. Organische Chemie, Universität des Saarlandes, Gebäude C 4.2, Saarbrücken, 66123, Germany

    Uli Kazmaier

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Poli, G., Prestat, G., Liron, F., Kammerer-Pentier, C. (2011). Selectivity in Palladium-Catalyzed Allylic Substitution. In: Kazmaier, U. (eds) Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis. Topics in Organometallic Chemistry, vol 38. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2011_14

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