Synthesis and structural features of α-acyloxy-(η3-allyl)palladium complexes

Kjellgren, Johan; Kritikos, Mikael; Szabó, Kálmán J.

doi:10.1016/j.jorganchem.2006.05.013

Cited by 2 publications

References 43 publications

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Cross‐Coupling with Organosilicon Compounds

et al. 2011

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Organosilicon functions possess many properties that make them ideal donors of organic groups in cross‐coupling reactions. Through the addition of an appropriate silicophilic Lewis base, an in situ pentacoordinate silane can effectively transfer an organic group. This feature allows for the rapid development of silicon cross‐coupling methods that continue today. Organosilicon‐based cross‐coupling has now become a practical, viable, and in some cases, superior compared with organoboron,‐zinc,‐tin couplings. The unique properties of organosilicon compounds provide a number of distinct advantages to their use as donors in transition‐metal catalyzed cross‐coupling reactions: 1, silicon moieties can be introduced into organic substrates by many general and high‐yielding methods for the construction of silicon carbon bonds; 2, organosilicon reagents are chemically robust and allow isolation and purification of products and are compatible with many functional groups; 3, silicon‐containing by‐products of the coupling are of low molecular weight, are nontoxic, and are easily removed from the reaction mixture; 4, a number of mild methods are available. This chapter presents a thorough overview of the various combinations of transferable groups and organic electrophiles. The scope is limited to the combination of silicon‐bearing nucleophiles with halo or related electrophiles under catalysis by palladium or nickel complexes wherein the silyl halide is lost.

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Cross‐Coupling with Organosilicon Compounds

et al. 2011

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Novel Substitutions of 1-Alkoxy- and 1-Arylsulfonyloxy-η³-allylmolybdenum Complexes. A Case for η¹-Alkenyl Carbene Complexes as Intermediates

et al. 2010

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A series of acyclic and cyclic 1-alkoxy-and 1-arylsulfonyloxy-substituted TpMo(CO) 2 (η 3 -allyl) complexes was synthesized and characterized, and exchange of the oxygenated substituent was investigated under a variety of reaction conditions. 1-Alkoxy-substituted η 3 -allyl and η 3 -butenyl complexes participated in direct, uncatalyzed exchange of the alkoxy substituent with benzylamine, but required a Lewis acid for exchange with alcohols. The 1-alkoxy-substituted η 3 -cyclohexenyl complex was unreactive towards exchange under all conditions investigated. The corresponding acyclic arylsulfonyloxy-substituted complexes underwent direct, uncatalyzed exchange with both benzylamine and alcohols, while the arylsulfonyloxy-substituted cyclohexenyl compounds participated in direct substitution with benzylamine, but not alcohols. High enantiopurity acyclic and cyclic alkoxy-and arylsulfonyloxy-substituted complexes provided exchange products with predominant, but incomplete, losses in enantiomeric excess in all cases examined. Mechanisms accounting for the observed reactivity trends and for the losses in enantiomeric excess are discussed. Reaction of alkoxy-substituted complexes through an associative mechanism and of arylsulfonyloxy-substituted compounds through a dissociative mechanism is suggested.

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Synthesis and structural features of α-acyloxy-(η3-allyl)palladium complexes

Cited by 2 publications

References 43 publications

Cross‐Coupling with Organosilicon Compounds

Cross‐Coupling with Organosilicon Compounds

Novel Substitutions of 1-Alkoxy- and 1-Arylsulfonyloxy-η³-allylmolybdenum Complexes. A Case for η¹-Alkenyl Carbene Complexes as Intermediates

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Synthesis and structural features of α-acyloxy-(η3-allyl)palladium complexes

Cited by 2 publications

References 43 publications

Cross‐Coupling with Organosilicon Compounds

Cross‐Coupling with Organosilicon Compounds

Novel Substitutions of 1-Alkoxy- and 1-Arylsulfonyloxy-η3-allylmolybdenum Complexes. A Case for η1-Alkenyl Carbene Complexes as Intermediates

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Novel Substitutions of 1-Alkoxy- and 1-Arylsulfonyloxy-η³-allylmolybdenum Complexes. A Case for η¹-Alkenyl Carbene Complexes as Intermediates