Solid Phase Organometallic Chemistry

Ljungdahl, Natalie; Bromfield, Karen M.; Kann, Nina

doi:10.1007/128_2007_125

Cited by 22 publications

(8 citation statements)

References 139 publications

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“…Solid-phase methodologies are deeply embedded in the synthesis of different biomolecules and inorganic materials and are increasingly used in the preparation of small organic molecules . At the same time, their potential in the field of organometallic synthesis is still largely untapped . Although the first attempts to advance and simplify cyclometalation, one of the most important fundamental organometallic transformations, using solvent-free strategies date back to the 1970s, before our investigations they have never been applied to the synthesis of such an exciting class of compounds as pincer complexes.…”

Section: Resultssupporting

confidence: 89%

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

et al. 2019

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1-Dimethylthiocarbamoyloxy-3-diphenylphosphinobenzene was used as a key precursor for the synthesis of a whole series of organophosphorus(V) pincer ligands combining thiocarbamate donor group with PX coordination arm, where X = S, Se, O, NR (R = Ph, 4-NO 2 C 6 H 4 , COO t Bu, CH 2 Ph) or CHR′ (R′ = COOEt, CN). Direct cyclopalladation of the ligands obtained (used either as individual compounds or generated in situ in the reaction mixture) afforded hybrid pincer complexes with fiveand sixmembered fused metallacycles. In the case of phosphine sulfide and phosphine selenide derivatives, the cyclopalladation can readily be accomplished in CH 2 Cl 2 at room temperature, leading to the target pincer complexes in high yields. Their phosphine imide and phosphonium ylide counterparts can also be obtained under mild reaction conditions, but the yields strongly depend on the ligand stability (35−93%). Even in the case of the phosphoryl-functionalized ligand, the desired pincer-type complex was synthesized in ca. 15% yield, although the main direction of metalation was C(sp 3 )−H bond activation of one of the methyl groups in OC(S)NMe 2 moiety. Realization of κ 3 -S,C,X-coordination (X = S, Se, O, N, or C) in the resulting pincer complexes was unambiguously confirmed based on the multinuclear NMR ( 1 H, 13 C, 31 P, and 77 Se) and IR spectroscopic data. Comparative single-crystal XRD analyses allowed for outlining the main structural features of the palladacycles obtained depending on the nature of ancillary P(V)-donor group. In addition, the possibility of solid-phase cyclopalladation was demonstrated by the examples of phosphine chalcogenide and stable phosphine imide ligands. In most cases, this approach afforded the desired complexes with the same or even higher efficiencies than the conventional solution-based method. Preliminary investigations on the cytotoxic activity of some of the complexes obtained against several human cancer cell lines revealed the high activity of phosphine imide-based palladacycles, rendering further studies in this field promising.

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Section: Resultssupporting

confidence: 89%

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

et al. 2019

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“…In addition, the concept of tin reagent grafted on a matrix has also been developed. This matrix can also be an imidazolium ionic liquid [32,33], a triarylphosphonium salt [34], a soluble polymer (which can be removed by precipitation) [35,36] or an insoluble macroporous polymer which can be separated by a simple filtration [37][38][39][40]. This last methodology is particularly well-suited for parallel and high-throughput syntheses which are widely developed for drug design in medicinal chemistry.…”

Section: Introductionmentioning

confidence: 99%

Use of polymer-supported phenyltin for the creation of aryl–aryl or aryl–heteroaryl bonds via Stille cross-coupling reactions

Kerric

Grognec

Zammattio

et al. 2010

Journal of Organometallic Chemistry

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“…Despite the interest in new indoles [ 3 – 5 ] and in particular for libraries of combinatorial compounds [ 2 , 6 – 17 ], there has only been one report for the application of the Bartoli reaction [ 18 – 23 ] on solid supports so far [ 24 ]. Organometallic reactions on solid supports are always particularly challenging [ 25 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of diverse indole libraries on polystyrene resin – Scope and limitations of an organometallic reaction on solid supports

Knepper¹,

Vanderheiden²,

Bräse³

2012

Beilstein J. Org. Chem.

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SummaryThe synthesis of diverse substituted indole structures on solid supports is described. The immobilization of nitrobenzoic acid onto Merrifield resin and the subsequent treatment with alkenyl Grignard reagents delivered indole carboxylates bound to solid supports. In contrast to results in the liquid phase, ortho,ortho-unsubstituted nitroarenes also delivered indole moieties in good yields. Subsequent palladium-catalyzed reactions (Suzuki, Heck, Sonogashira, Stille) delivered, after cleavage, the desired molecules in moderate to good yields over four steps. The scope and limitations are presented.

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Solid Phase Organometallic Chemistry

Cited by 22 publications

References 139 publications

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

Extending the Application Scope of Organophosphorus(V) Compounds in Palladium(II) Pincer Chemistry

Use of polymer-supported phenyltin for the creation of aryl–aryl or aryl–heteroaryl bonds via Stille cross-coupling reactions

Synthesis of diverse indole libraries on polystyrene resin – Scope and limitations of an organometallic reaction on solid supports

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