Synthesis of secondary α-perfluoroalkyl- and tertiary α,α-bis(perfluoroalkyl)-N-methylprolinols and their catalytic activities in the acyl transfer reaction

Funabiki, Kazumasa; Shibata, Akitsugu; Hatano, K.; Matsui, Masaki

doi:10.1016/j.jfluchem.2009.02.002

Cited by 6 publications

(1 citation statement)

References 23 publications

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“…However, to the best of our knowledge, there has been only one report on the remarkable effects of long fluoroalkyl (fluorous) groups in asymmetric organocatalysts on the yield and no report on diastereo‐ and/or enantioselectivity in catalytic reactions,6 although the introduction of long fluoroalkyl (fluorous) groups into organocatalysts has been established as one of the most promising methods for the easy recovery and reuse of organocatalysts by using a fluorous separation technology developed by Curran et al 7…”

Section: Introductionmentioning

confidence: 99%

Conditions Favoring the Formation of Monomeric Pt^III Derivatives in the Electrochemical Oxidation of trans‐[Pt^II{(p‐BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)]

et al. 2015

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Characterization of the anticancer active compound trans‐[PtII{(p‐BrC6F4)NCH2CH2NEt2}Cl(py)] is described along with identification of electrochemical conditions that favor formation of a monomeric one‐electron‐oxidized PtIII derivative. The square‐planar organoamidoplatinum(II) compound was synthesized through a carbon dioxide elimination reaction. Structural characterization by using single‐crystal X‐Ray diffraction reveals a trans configuration with respect to donor atoms of like charges. As PtIII intermediates have been implicated in the reactions of platinum anticancer agents, electrochemical conditions favoring the formation of one‐electron‐oxidized species were sought. Transient cyclic voltammetry at fast scan rates or steady‐state rotating disc and microelectrode techniques in a range of molecular solvents and an ionic liquid confirm the existence of a well‐defined, chemically and electrochemically reversible one‐electron oxidation process that, under suitable conditions, generates a PtIII complex, which is proposed to be monomeric [PtIII{(p‐BrC6F4)NCH2CH2NEt2}Cl(py)]+. Electron paramagnetic resonance spectra obtained from highly non‐coordinating dichloromethane/([Bu4N][B(C6F5)4]) solutions, frozen to liquid nitrogen temperature immediately after bulk electrolysis in a glove box, support the PtIII assignment rather than formation of a PtII cation radical. However, the voltammetric behavior is highly dependent on the timescale of the experiments, temperature, concentration of trans‐[PtII{(p‐BrC6F4)NCH2CH2NEt2}‐ Cl(py)], and the solvent/electrolyte. In the low‐polarity solvent CH2Cl2 containing the very weakly coordinating electrolyte [Bu4N][B(C6F5)4], a well‐defined reversible one‐electron oxidation process is observed on relatively long timescales, which is consistent with the stabilization of the cationic platinum(III) complex in non‐coordinating media. Bulk electrolysis of low concentrations of [Pt{(p‐BrC6F4)NCH2CH2NEt2}Cl(py)] favors the formation of monomeric [PtIII{(p‐BrC6F4)NCH2CH2NEt2}Cl(py)]+. Simulations allow the reversible potential of the PtII/PtIII process and the diffusion coefficient of [PtIII{(p‐BrC6F4)‐ NCH2CH2NEt2}Cl(py)]+ to be calculated. Reversible electrochemical behavior, giving rise to monomeric platinum(III) derivatives, is rare in the field of platinum chemistry.

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Section: Introductionmentioning

confidence: 99%

Conditions Favoring the Formation of Monomeric Pt^III Derivatives in the Electrochemical Oxidation of trans‐[Pt^II{(p‐BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)]

et al. 2015

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High Diastereoselectivity Induced by a Fluorous Alkyl Group in the Asymmetric Michael Reaction of Nitroalkenes Catalyzed by a Prolinol Methyl Ether

et al. 2013

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The fluorous prolinol methyl ether was prepared through the perfluorohexylethylation of (S)‐1‐tert‐butyl 2‐methyl pyrrolidine‐1,2‐dicarboxylate using commercially available perfluorohexylethyl iodide, methylation, and deprotection in three steps in 19 % overall yield. In the asymmetric Michael addition reaction of nitrostyrene with propanal, the diastereoselectivity (syn/anti=92:8) with the prepared fluorous prolinol methyl ether was much higher than that (syn/anti=87–80:13–20) with nonfluorinated prolinol methyl ethers that have two n‐octyl groups or two phenyl groups in place of perfluorohexylethyl groups.

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ChemInform Abstract: Synthesis of Secondary α‐Perfluoroalkyl‐ and Tertiary α,α‐Bis(perfluoroalkyl)‐N‐methylprolinols and Their Catalytic Activities in the Acyl Transfer Reaction.

et al. 2009

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Synthesis of secondary α-perfluoroalkyl- and tertiary α,α-bis(perfluoroalkyl)-N-methylprolinols and their catalytic activities in the acyl transfer reaction

Cited by 6 publications

References 23 publications

Conditions Favoring the Formation of Monomeric Pt^III Derivatives in the Electrochemical Oxidation of trans‐[Pt^II{(p‐BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)]

Conditions Favoring the Formation of Monomeric Pt^III Derivatives in the Electrochemical Oxidation of trans‐[Pt^II{(p‐BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)]

High Diastereoselectivity Induced by a Fluorous Alkyl Group in the Asymmetric Michael Reaction of Nitroalkenes Catalyzed by a Prolinol Methyl Ether

ChemInform Abstract: Synthesis of Secondary α‐Perfluoroalkyl‐ and Tertiary α,α‐Bis(perfluoroalkyl)‐N‐methylprolinols and Their Catalytic Activities in the Acyl Transfer Reaction.

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Synthesis of secondary α-perfluoroalkyl- and tertiary α,α-bis(perfluoroalkyl)-N-methylprolinols and their catalytic activities in the acyl transfer reaction

Cited by 6 publications

References 23 publications

Conditions Favoring the Formation of Monomeric PtIII Derivatives in the Electrochemical Oxidation of trans‐[PtII{(p‐BrC6F4)NCH2CH2NEt2}Cl(py)]

Conditions Favoring the Formation of Monomeric PtIII Derivatives in the Electrochemical Oxidation of trans‐[PtII{(p‐BrC6F4)NCH2CH2NEt2}Cl(py)]

High Diastereoselectivity Induced by a Fluorous Alkyl Group in the Asymmetric Michael Reaction of Nitroalkenes Catalyzed by a Prolinol Methyl Ether

ChemInform Abstract: Synthesis of Secondary α‐Perfluoroalkyl‐ and Tertiary α,α‐Bis(perfluoroalkyl)‐N‐methylprolinols and Their Catalytic Activities in the Acyl Transfer Reaction.

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Conditions Favoring the Formation of Monomeric Pt^III Derivatives in the Electrochemical Oxidation of trans‐[Pt^II{(p‐BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)]

Conditions Favoring the Formation of Monomeric Pt^III Derivatives in the Electrochemical Oxidation of trans‐[Pt^II{(p‐BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)]