Palladium(0) mediated coupling of bromophosphaalkenes with Grignard reagents

Sluis, M. van der; Klootwijk, A.; Wit, Jan B. M.; Bickelhaupt, F.; Veldman, Nora; Spek, Anthony L.; Jolly, P. W.

doi:10.1016/s0022-328x(96)06445-5

Cited by 32 publications

(34 citation statements)

References 33 publications

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“… a) Synthetic approaches to π‐extended phosphaalkenes: i) Condensation process, ii) Nucleophilic substitution process, iii) Cross‐coupling process. b) Undesirable 1,2‐rearrangement for the cross‐coupling process …”

Section: Figurementioning

confidence: 99%

Palladium-Catalyzed Arylation of a Sterically Demandinggem-Dibromophosphaethene

2016

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Dedicated to Prof. Masaaki Yoshifuji on the occasion of his 75th birthdayThe trans bromide of 2,2-dibromo-1-(2,4,6-tri-t-butylphenyl)-1phosphaethene (Mes*P=CBr 2 ; Mes* = 2,4,6-tBu 3 C 6 H 2 ) can be successfully substituted with an aryl group by using a palladium version of the Kumada-Tamao-Corriu cross-coupling process. Predominant formation of the 2-aryl-2-bromo-1-phosphaethene [(Z)-Mes*P=C(Br)Ar] required suitable conditions including optimization of the ancillary phosphine ligand, thereby retarding the dual elimination of bromides leading to phosphaalkyne (Mes*C P). The 2-aryl-2-bromo-1-phosphaethenes hold promise as versatile synthons for functional p-conjugated molecules, and stereospecific transformations of the bromine atom by halogen-metal exchange and palladium-catalyzed arylations were demonstrated.[a] Prof.

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Section: Figurementioning

confidence: 99%

Palladium-Catalyzed Arylation of a Sterically Demandinggem-Dibromophosphaethene

2016

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“…Analysis of aC DCl 3 solution of the crude product by 31 P{ 1 H} NMR spectroscopy did not show as harp signal that could be assigned to the 1-phospha-1,3-butadiene monomer (d = 271 ppm). [14] Only broad signals were observed which, combined with the viscous nature of the solution, were suggestive of apolymer.Following additional purification and precipitation steps,t he polymeric product, 2,w as isolated as ay ellow glass.I mportantly,a nalysis of this isolated material by GPC-MALS ( Figure S4 in the Supporting Information (SI)) confirmed the polymeric nature of 2 (M n = 6000 gmol À1 ; M = 1.07). It is plausible that the narrow polydispersity is ac onsequence of fractionation of the polymer during the extensive work-up and/or an anionic polymerization mechanism initiated by excess vinylmagnesium bromide.…”

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confidence: 95%

“…[5][6][7] In particular, the homo-and co-polymerization of the mono-phosphaalkene MesP=CPh 2 has led to functional materials that are useful as catalyst supports,a s templates for self-assemblies,a nd as potential luminescent sensors. [8] We now turn our attention to the potential use of rare molecules with both P = Ca nd C = Cb onds [9][10][11][12][13][14][15] as monomers for polymerization studies.…”

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confidence: 99%

“…As ap otential monomer for polymerization studies,t he known P-Mes*-substituted 1-phospha-1,3-butadiene (Mes* = 2,4,6-tri-tert-butylphenyl) caught our attention. [14] Interestingly,the authors referred to the "instability of 1-phospha-1,3butadiene which tends to polymerize." No details of the postulated "polymers" were provided.…”

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confidence: 99%

“…No details of the postulated "polymers" were provided. Using ah ybrid of the procedures reported for 1-phospha-1,3-butadiene and 1phosphaisoprene, [14,15] aT HF solution of bromophosphaalkene 1 was treated with vinylmagnesium bromide in the presence of [Pd(PPh 3 ) 4 ](Scheme 1). After 24 h, methanol was added and the crude product was isolated as aviscous brown oil.…”

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Polymerization of 1‐Phosphaisoprene: Synthesis and Characterization of a Chemically Functional Phosphorus Version of Natural Rubber

et al. 2017

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Macromolecules derived from 1,3-dienes, such as polyisoprene (or natural rubber), are of considerable importance in polymer science. Given the parallels between P=C and C=C bonds, the prospect of polymerizing P-containing 1,3-dienes, such as 1-phosphaisoprene, is intriguing due to the unique chemical functionality imparted by the heavier element combined with their structural relationship to natural rubber. Herein, we report the synthesis, characterization and coordination chemistry of the first polymers derived from Mes*P=CR-CH=CH (Mes*=2,4,6-t-Bu C H ; R=H, Me). In the case of 1-phosphaisoprene (R=Me), the monomer is isolable and its anionic polymerization affords a polymer that retains P=C bonds in its microstructure. The chemical functionality of these novel materials is demonstrated by forming the macromolecular gold(I) complex where the P=C bond is retained for further chemical elaboration.

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Incorporating Phosphaalkenes into Oligoacetylenes

et al. 2008

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Eine Verkleinerung der HOMO‐LUMO‐Bandlücke um 0.5 eV wird beobachtet, wenn die beiden terminalen Kohlenstoffatome eines Tetrain‐verknüpften Bisalkens durch zwei Phosphorzentren ersetzt werden. Die acetylenischen Phosphaalkene sind aus einem ambivalenten Carben‐artigen C5‐Intermediat zugänglich und eignen sich für den Aufbau komplexer phosphor‐ und kohlenstoffreicher Moleküle (siehe Bild; C grau, P violett).

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Palladium(0) mediated coupling of bromophosphaalkenes with Grignard reagents

Cited by 32 publications

References 33 publications

Palladium-Catalyzed Arylation of a Sterically Demandinggem-Dibromophosphaethene

Palladium-Catalyzed Arylation of a Sterically Demandinggem-Dibromophosphaethene

Polymerization of 1‐Phosphaisoprene: Synthesis and Characterization of a Chemically Functional Phosphorus Version of Natural Rubber

Incorporating Phosphaalkenes into Oligoacetylenes

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