Dicarbonyl pentaphenylcyclopentadienyl iron complex for living radical polymerization: Smooth generation of real active catalysts collaborating with phosphine ligand

Ishio, Muneki; Ouchi, Makoto; Sawamoto, Mitsuo

doi:10.1002/pola.24468

Cited by 9 publications

(8 citation statements)

References 41 publications

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“…Our group has developed some iron catalysts, e.g., FeCl 2 (PPh 3 ) 2 , or the related iron-based systems for LRP. ,− Various ligands or additives in conjunction with FeX 2 or FeX 3 (X: halogen) have been also reported by other groups: halide anion (e.g., tetrabutylammonium bromide), polar solvent (e.g., N -methylpyrrolidone), phosphine–pyridine hybrid ligand, high electron-donating phosphine ligand, etc. One example of recent progress in iron catalysis is using decamethylferrocene as a cocatalyst for iron catalytic system with FeBr 2 / n -Bu 4 NBr (Figure b), which was derived from ferrocene cocatalysis in ruthenium-catalyzed LRP as described above .…”

Section: Recent Development Of Metal-catalyzed Lrpmentioning

confidence: 99%

50th Anniversary Perspective: Metal-Catalyzed Living Radical Polymerization: Discovery and Perspective

2017

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Development of living polymerizations via reversible activation of dormant species opened the door to discovery of metal-catalyzed living radical polymerization that is now very useful for precise construction of tailor-made polymeric architectures. In this commemorative Perspective, the historical aspects as well as the prospects as a new polymerization tool are described toward advanced structural control or technological materials innovation in various fields.

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Section: Recent Development Of Metal-catalyzed Lrpmentioning

confidence: 99%

50th Anniversary Perspective: Metal-Catalyzed Living Radical Polymerization: Discovery and Perspective

2017

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“…Therefore, for the synthesis of biomaterials using ATRP method, it is a better choice to use the nontoxic or low‐toxic iron catalyst instead of a heavy metal (e.g., copper) although iron complexes were generally considered to be inferior to copper complexes for the control of polymerization 31. Actually, a variety of iron complexes have been developed for iron‐mediated ATRP of hydrophobic monomers (i.e., styrene, methyl methacrylate)47–64 since the first case catalyzed by FeCl 2 (PPh 3 ) 2 complex in 1997 65. However, most of iron catalysts are unable to catalyze ATRP of functional monomers effectively as a result of their interaction with polar groups of monomers.…”

Section: Introductionmentioning

confidence: 99%

Upfront observation versus radiation for adult pilocytic astrocytoma

Ishkanian

Laperrière

et al. 2011

Cancer

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BACKGROUND: Although pilocytic astrocytoma accounts for up to 40% of all childhood brain tumors, it is a rare disease in adults. Consequently, there are few mature data on the impact of up-front treatment options after surgery that include observation or adjuvant radiotherapy. METHODS: Ten women and 20 men were identified who were diagnosed with pilocytic astrocytoma from 1971 to 2007 and were retrospectively reviewed. The median patient age was 30 years (range, 18-64 years), and the median follow-up was 87 months (range, 16-420 months). Initial surgery included biopsy (10% of patients), subtotal resection (57% of patients), or gross-total resection (33% of patients). Nineteen patients were observed postoperatively, whereas 11 patients received up-front postoperative adjuvant radiotherapy (50 grays in 25 fractions). No patient received adjuvant or concurrent chemotherapy. Progression-free survival (PFS) and overall survival (OS) were calculated using the Kaplan-Meier method. Differences between survival curves were analyzed with the log-rank test. RESULTS: For the entire cohort, the 5-year and 10-year OS rates were 95% and 85%, respectively, and the 5-year and 10-year PFS rates were 63% and 35%, respectively. The median PFS was 8.4 years. Initial radiation, compared with observation, did not have an impact on OS but significantly improved PFS. The 5-year PFS rate for patients who were observed versus those who received radiation was 42% versus 91%, respectively; and, at 10 years, the PFS rate was 17% versus 60%, respectively (P ¼ .005). Patients who progressed after observation (11 of 19 patients) received various salvage therapies, resulting in a 2-year PFS rate of 68% compared with 33% for patients who progressed after initial radiation (3 of 11 patients) and were salvaged with either chemotherapy or surgery (P ¼ .1). CONCLUSIONS: Adjuvant radiotherapy for pilocytic astrocytoma significantly prolonged PFS at both 5 years and 10 years compared with observation. However, equivalent OS was observed, which reflected the efficacy of salvage therapies. Cancer 2011;117:4070-

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“…The polymerization of vinyl acetate (VAc) was also successfully performed with Cp 2 (CO) 4 Fe 2 as catalyst. 282 In addition, Sawamoto et al 283 iron catalysts with carbonyl-phosphine heteroligation, namely, CpFe(CO)(L Phos )Br or Cp*Fe(CO)(L Phos )Br (L Phos = TPP, TBP, DPMP, DMPP, T m TP, or T p TP), were prepared by the reactions of CpFe(CO) 2 Br or Cp*Fe(CO) 2 Br with phosphine under UVirradiation, 284,285 and they were found to be active and efficient catalysts for the ATRPs of MMA, MA and PEGMA. Cp*Fe(CO)(L Phos )Br showed a better controllability of MA and PEGMA polymerizations than CpFe(CO)(L Phos )Br.…”

Section: Isolated Iron Complexesmentioning

confidence: 99%

“…The polymerization of vinyl acetate (VAc) was also successfully performed with Cp 2 (CO) 4 Fe 2 as catalyst 282. In addition, Sawamoto et al283 used the dicarbonyl complex Cp Ph Fe(CO) 2 Br for the iron-catalyzed ATRP of MMA in the 70 presence of catalytic amount of phosphine (TPP, TBP, DPMP, dimethylphenylphosphine (DMPP), or tri-m-tolylphosphine (T m TP)), producing controlled PMMA with predictable molecular weights and narrow MWDs. Notably, the real catalyst for polymerization was phosphine iron catalyst.…”

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confidence: 99%

Iron-catalyzed atom transfer radical polymerization

2015

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In the last two decades, metal-catalyzed controlled radical polymerization (CRP), or atom transfer radical 5 polymerization (ATRP) has become a ubiquitous tool for the facile synthesis of a wide of materials with specific macromolecular architectures. The complex plays an important role in ATRP, and for this purpose researchers put a great deal of effort on studying the effect of various complexes on polymerization. However, one of disadvantages of copper complex which is the most extensively studied catalyst system in ATRP is the contamination of polymers resulted from a high concentration of stable catalyst. 10 Efficiently and economically removing the catalyst from the resultant polymers will open the way to a wide variety of new functional polymers for specialty applications, especially for large-scale industrial manufacture. Iron-based catalysts have attracted particular attention because of their low toxicity, low cost, abundance, and environmental friendliness, and thus many iron catalysts have been designed for ATRP. This article reviews the preparation of polymers using iron-catalyzed atom transfer radical 15 polymerization, and is organized according to: (a) mechanistic considerations; (b) Iron complexes and ligand types.

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Dicarbonyl pentaphenylcyclopentadienyl iron complex for living radical polymerization: Smooth generation of real active catalysts collaborating with phosphine ligand

Cited by 9 publications

References 41 publications

50th Anniversary Perspective: Metal-Catalyzed Living Radical Polymerization: Discovery and Perspective

50th Anniversary Perspective: Metal-Catalyzed Living Radical Polymerization: Discovery and Perspective

Upfront observation versus radiation for adult pilocytic astrocytoma

Iron-catalyzed atom transfer radical polymerization

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