A structure–activity relationship for pincer palladium(II) complexes—influence of ring-size of metallacycles on the activity in allylic alkylation

Wang, Zhaohui; Eberhard, Michael R.; Jensen, Craig M.; Matsukawa, Shiro; Yamamoto, Yohsuke

doi:10.1016/s0022-328x(03)00604-1

Cited by 58 publications

(31 citation statements)

References 37 publications

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“…Nowadays, hybrid systems bearing donor groups of different nature are of particular interest since they offer additional possibilities for fine-tuning electronic and steric properties. Pincer metallacycles based on such unsymmetrical ligands were shown to combine characteristics of several symmetrical prototypes or manifest unique properties [8,12,[74][75][76][77]. Despite an increasing number of publications devoted to the hybrid pincer complexes, only several examples containing thione sulfur donors have been described to date.…”

Section: Hybrid Pincer Compounds With Thione Sulfur Donorsmentioning

confidence: 99%

Pincer Complexes with Thione Sulfur Donors

Aleksanyan

Козлов

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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Rapid development of pincer chemistry over the last several decades made a substantial contribution in extension of theoretical and practical organometallic chemistry as well as organic synthesis, catalysis, and materials science. This review is devoted to relatively new types of nonclassical pincer compounds bearing thione sulfur donors incorporated into thiophosphoryl and/or thioamide groups. The discussion is focused on synthetic aspects and structural features of symmetrical and hybrid S,C,S-pincer ligands and complexes with particular attention to the practically valuable properties.

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Section: Hybrid Pincer Compounds With Thione Sulfur Donorsmentioning

confidence: 99%

Pincer Complexes with Thione Sulfur Donors

Aleksanyan

Козлов

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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“…[13,32,33] Catalytic Investigations: Batch Reactions PCP complexes have shown good to excellent activities in the palladium-catalyzed Heck and Suzuki couplings, [34,35] hydroamination, [36] ruthenium-catalyzed transfer hydrogenation, [37] and iridium-catalyzed dehydrogenation. [38] We were interested in the application of the supported phosphine ligands 13-15 in the palladium-catalyzed allylic alkylation [39] and in the allylic amination reaction. These reactions find applications in total synthesis reactions [40] as well as in the synthesis of amino acids, alkaloids, or carbohydrate derivatives by transformation of the allyl amines produced by the allylic amination reaction.…”

Section: Preparation Of Palladium Complexesmentioning

confidence: 99%

Molecular‐Weight‐Enlarged Multiple‐Pincer Ligands: Synthesis and Application in Palladium‐Catalyzed Allylic Substitution Reactions

et al. 2009

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Three different pincer ligand systems are synthesized via nucleophilic substitution reactions of polyaromatic benzyl bromides as support molecules and phenol derivatives as ligand precursors. Retention tests using a polymeric nanofiltration membrane show moderate to good retention in THF and CH(2)Cl(2). Concentration-dependent NMR spectroscopy gives no indication for the formation of aggregates in solution. The three ligand systems are active in both the allylic alkylation and allylic amination reactions and show high selectivity towards the linear trans products. An investigation of the kinetic parameters of the allylic amination reaction show that the reaction of cinnamyl acetate with morpholine is of zero order in cinnamyl acetate and of first order in morpholine. The order in catalyst is found to be one, and the rate constant k' is determined for a reaction under standard conditions. Moreover, one of the tri(pincer)-palladium complexes is used as soluble, molecular-weight-enlarged homogeneous catalyst in continuous allylic alkylation and amination reactions. The conversion of the allylic alkylation reaches a maximum of 30 %, while a maximum conversion of 80 % is reached in the allylic amination reaction. No palladium black was formed.

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“…; the first pincer complex containing both five-and six-membered metallacycles [8]. Venanzi et al synthesised [MBr{(C 6 H 3 )((CH 2 ) 2 PPh 2 ) 2 -2,6}] (M 0/Pd, Pt), the only example of a PCP pincer complex with two sixmembered metallacycles [9].…”

Section: Ligand and Complex Synthesismentioning

confidence: 99%

“…13 C{ 1 H}-NMR (75 MHz, CDCl 3 ): d 0/ 17.0, 17.7, 17.8, 28.6, 28.6, 28. 8,28.9,29.4,29.5,29.9,30.5,34.0,34.3,35.43,35.6,109.6 (d,J 0/15.5 Hz),118.7 (d,J 0/19.8 Hz),126.7,144.0,152.1 (d,J 0/18.4 Hz),166.4 (d,J0/13.1 Hz). 31 P{ 1 H}-NMR (121 MHz, CD 2 Cl 2 ): d0/73.6 (d, J 0/388 Hz, P t Bu 2 ), 187.1 (d, J 0/388 Hz, OP i Pr 2 ).…”

Section: General Proceduresmentioning

confidence: 99%