Synthesis of Optically Active Polymer with P‐Stereogenic Phosphine Units

Morisaki, Yasuhiro; Suzuki, Kentaro; Imoto, Hiroaki; Chujo, Yoshiki

doi:10.1002/marc.201000237

Cited by 16 publications

(10 citation statements)

References 63 publications

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“…reported the synthesis of 3 by reacting 3,5‐dibromophenol with 1‐bromododecane in the presence of K 2 CO 3 (as base) and dimethyl ketone as solvent. The reaction mixture was refluxed for 18 h and the yield of the reaction was 84% . We observed that if 3,5‐dibromophenol and K 2 CO 3 are allowed to stir in DMF for 1 h followed by dropwise addition of n ‐dodecyl bromide and stirring the reaction mixture at 75 °C, the formation of the desired 3 is almost quantitative in 2 h (Scheme ).…”

Section: Resultsmentioning

confidence: 95%

Triptycene‐based fluorescent polymers with pendant alkyl chains: interaction with fullerenes and morphology of thin films

Ansari

Mallik

Mondal

et al. 2018

Polymer International

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We report unique triptycene‐based alternating copolymers bearing long alkyl chains as pendants. Syntheses utilized 2,6‐diethynyltriptycene and appropriate alkyloxyarene monomers polymerized via Sonogashira cross‐coupling reaction to yield triptycene‐based poly(phenylene ethynylene)s. Resulting polymers are soluble in organic solvents and were characterized using various techniques. Experimental results suggest the polymers are thermally stable and fluorescent. The fluorescence emission is quenched in the presence of fullerenes (C60 and C70) suggesting strong host–guest interactions. The magnitude of the binding constant between the polymers and these fullerenes was determined to be of the order of 105 mol L−1. The effects of chain length on the morphology and wettability of the polymers on silicon substrates were studied using atomic force microscopy. Three distinct dewetting patterns, i.e. spherical domains, fractal structures and ring structures, were observed with variation in the pendant chain length. This ability to control the thin‐film morphology of the polymers may have potential technological applications, which include but are not limited to sensors, fluorescent coatings and organic electronics. © 2018 Society of Chemical Industry

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Section: Resultsmentioning

confidence: 95%

Triptycene‐based fluorescent polymers with pendant alkyl chains: interaction with fullerenes and morphology of thin films

Ansari

Mallik

Mondal

et al. 2018

Polymer International

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“…We attempted to remove the boranes coordinated with the phosphorus atoms in tetraphosphine (S,R,R,S)-8 ÀBH 3 by using organic bases such as morpholine 23 [11][12][13] ). When (S,R,R,S)-8 ÀBH 3 was stirred in morpholine for 48 h, all the boranes were readily removed.…”

Section: P-stereogenic Oligophosphinesmentioning

confidence: 99%

“…[2][3][4][5][6] However, despite the widespread use of P-stereogenic phosphines, polymers containing chiral phosphorus atoms in their backbones have rarely been prepared. 7 Recently, we synthesized P-stereogenic optically active polymers [8][9][10][11][12][13] and oligomers [14][15][16] using P-stereogenic bisphosphines as chiral building blocks. These molecules formed higher-ordered chiral structures derived from P-stereogenic centers, and their conformations could be controlled through metal coordination with bisphosphine moieties.…”

Section: Introductionmentioning

confidence: 99%

“…These molecules formed higher-ordered chiral structures derived from P-stereogenic centers, and their conformations could be controlled through metal coordination with bisphosphine moieties. [11][12][13] On the other hand, well-defined oligophosphines could potentially be used as platforms for binding transition metals in an orderly fashion. Several types of optically active P-stereogenic oligophosphines have already been prepared ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of unsymmetrical P-stereogenic oligophosphines and chemoselective cleavage of phosphine-borane coordinate bonds

Imoto

Kato

Morisaki

et al. 2012

Polym J

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This paper describes the synthetic details and coordination abilities of optically active P-stereogenic tetraphosphine and hexaphosphine with different substituted groups on their phosphorus atoms. The polymers consist of two types of phosphine units, that is, tert-butyl-and phenylphosphines. The boranes on the phenylphosphine moieties were chemoselectively removed by organic base such as diazabicyclo[2. Keywords: chemoselectivity; coordination; oligomer; P-chirality INTRODUCTION Phosphorus atom is a unique element in its ability to create chiral architectures because a trivalent phosphorus atom can adopt a conformationally stable tetrahedral structure arising from its high inversion energy. 1 In fact, several such P-stereogenic phosphines have been prepared, and in particular, P-stereogenic bisphosphines have been widely employed as chelate ligands for transition metal-catalyzed asymmetric reactions. [2][3][4][5][6] However, despite the widespread use of P-stereogenic phosphines, polymers containing chiral phosphorus atoms in their backbones have rarely been prepared. 7 Recently, we synthesized P-stereogenic optically active polymers 8-13 and oligomers 14-16 using P-stereogenic bisphosphines as chiral building blocks. These molecules formed higher-ordered chiral structures derived from P-stereogenic centers, and their conformations could be controlled through metal coordination with bisphosphine moieties. [11][12][13] On the other hand, well-defined oligophosphines could potentially be used as platforms for binding transition metals in an orderly fashion. Several types of optically active P-stereogenic oligophosphines have already been prepared (Figure 1). Wild and co-workers reported the syntheses and coordination behaviors of optically active P-stereogenic tetraphosphines and hexaphosphines, which were obtained by separating a mixture of stereoisomers by column chromatography and successive complexation with chiral palladium complexes. [17][18][19][20][21][22][23] Our group 14-16 and Imamoto's group 24-29 independently succeeded in synthesizing optically active P-stereogenic tetraphosphines (Figure 1) through different synthetic routes. Imamoto et al. 28 prepared their transition metal complexes, and the obtained complexes were used as chiral catalysts for transition metal-catalyzed asymmetric hydrogenations.

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“…Recently, we have focused on P‐stereogenic bisphosphines ( S,S )‐ 1 –BH 3 and ( S,S )‐ 2 –BH 3 , which were reported by Evans28 and Imamoto,29 respectively, as building blocks for optically active cyclic compounds,30–32 oligomers,33–35 dendrimers,36 and polymers 37–41. The incorporation of the P‐stereogenic bisphosphines into the polymer main chain leads to the construction of optically active polymers.…”

Section: Introductionmentioning

confidence: 99%

P‐Stereogenic Optically Active Polymer and the Complexation Behavior

Morisaki

Suzuki

Imoto

et al. 2011

Macro Chemistry & Physics

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The synthetic details of the P-stereogenic optically active polymer and the complexation behavior with palladium and platinum complexes are reported. The polymer consists of P-stereogenic bisphosphine units and the conjugated phenylene-ethynylene units alternately. The P-stereogenic bisphosphine moieties can coordinate to transition metals such as palladium and platinum, leading to a change in the conformation. optically active polymers. In a previous communication, we reported the synthesis of optically active polymers consisting of P-stereogenic bisphosphine and mphenylene-ethynylene units in the main chain by using ( S,S )-1 -BH 3 as a monomer and investigated the complexation with palladium. [ 40 ] In this article, we disclose the synthetic procedure of the P-stereogenic optically active poly mer and discuss the complexation behavior of the polymers with palladium and platinum in detail. Results and DiscussionThe synthesis of the key monomer ( S,S )-3 -BH 3 is outlined in Scheme 1 . Methyl groups in ( S,S )-1a -BH 3 can be readily lithiated thanks to the electron-withdrawing feature of the coordinated BH 3 . The treatment of ( S,S )-1 -BH 3 with sec -BuLi and N , N , N ′ , N ′ -tetramethylethylenediamine (TMEDA) in THF at -78 ° C provided the dilithiated intermediate, which was reacted in situ with 3-(bromomethyl)-1-iodobenzene at room temperature to obtain the corresponding P-stereogenic enantiomerically pure compound ( S,S )-3 -BH 3 in 59% isolated yield. The enantiomeric purity was maintained during the reactions, because the reactions do not include an asymmetric process. 3,5-Diethynyl-1-dodecyloxybenzene ( 7 ) was synthesized as a comonomer, as shown in Scheme 2 . The reaction of 3,5-dibromophenol ( 4 ) with 1-bromododecane in the presence of K 2 CO 3 in acetone afforded the 3,5-dibromo-1-dodecyloxybenzene ( 5 ) in 84% isolated yield. Sonogashira-Hagihara coupling [ 42 ] of 4 with trimethylsilylacetylene was carried out by a PdCl 2 (PPh 3 ) 2 /

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Synthesis of Optically Active Polymer with P‐Stereogenic Phosphine Units

Cited by 16 publications

References 63 publications

Triptycene‐based fluorescent polymers with pendant alkyl chains: interaction with fullerenes and morphology of thin films

Triptycene‐based fluorescent polymers with pendant alkyl chains: interaction with fullerenes and morphology of thin films

Synthesis of unsymmetrical P-stereogenic oligophosphines and chemoselective cleavage of phosphine-borane coordinate bonds

P‐Stereogenic Optically Active Polymer and the Complexation Behavior

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