Optically active helical polyisocyanides bearing chiral phosphine pendants: Facile synthesis and application in enantioselective Rauhut-Currier reaction

Zhou, Li; Shen, Ling; Huang, Jian; Liu, Na; Zhu, Yuan‐Yuan; Wu, Zong‐Quan

doi:10.1007/s10118-018-2044-8

Cited by 25 publications

(19 citation statements)

References 35 publications

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“…[40][41][42][43] In addition to this field advanced chiral polymers have been synthesized with grafted optically active helical polymeric structures and has been applied to chiral recognition. [44][45][46][47][48] Here we focus on an important question that has not been explored in details in the field of chiral polymeric particles whether the chiral composition of the polymeric particles affects their chiral recognition. Most studies involve chiral particles with a single chiral function, for example one chiral monomer of one chiral group, rather than multiple chiral functions.…”

Section: Doi: 101002/macp202000328mentioning

confidence: 99%

Synthesis of Multi Amino Acid Chiral Polymeric Microparticles for Enantioselective Chemistry

Abuaf

Mastai

2020

Macro Chemistry & Physics

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Chiral polymeric particles have emerged as a new and exciting field of research and in the last years due to their possible use for many applications in chiral chemistry. In this article, an important question is focused upon that has not been explored in detail in the field of chiral polymeric particles. The main question is whether the chiral composition of the polymeric particles affects their chiral recognition. The hypothesis is that chiral polymeric particles with a variety of different chiral groups will improve chiral recognition and improve their use of enantioselectivity crystallization. Consequently, chiral microparticles based on one up to three different amino acids based monomers are prepared by precipitation polymerization. The chiral microspheres are characterized by dynamic light scattering, scanning electron microscope (SEM), mass spectrometry (MS), and nuclear magnetic resonance (NMR) and display a narrow size distribution in the range of 1–2 μm. The chiral discrimination ability of these chiral microspheres for enantioselective crystallization is studied in the crystallization of DL‐leucine crystallization, as a model system. Time‐resolved polarimetry, X‐ray diffraction (XRD), and differential scanning calorimetry (DSC) are used to provide evidence for enantioselective crystallization. Surprisingly the results show that only particles composed of one amino acids monomers show the best results for enantioselective crystallization.

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Section: Doi: 101002/macp202000328mentioning

confidence: 99%

Synthesis of Multi Amino Acid Chiral Polymeric Microparticles for Enantioselective Chemistry

Abuaf

Mastai

2020

Macro Chemistry & Physics

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“…The molecular design and synthesis of multifunctional polymeric materials have received much attention because of their favorable properties in a variety of fields [1,2,3,4,5,6]. Among them, photoresponsive polymers comprising azobenzene chromophores are of great scientific interest because of their potential application in optical data storage, holographic recording, and surface-relief gratings [7,8,9,10,11].…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bonding-Induced Assembled Structures and Photoresponsive Behavior of Azobenzene Molecule/Polyethylene Glycol Complexes

et al. 2019

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We investigated the self-assembled structures and photoresponsive and crystallization behaviors of supramolecules composed of 4-methoxy-4′-hydroxyazobenzene (Azo) molecules and polyethylene glycol (PEG) that were formed through hydrogen-bonding interactions. The Azo/PEG complexes exhibited the characteristics of photoresponse and crystallization, which originated from Azo and PEG, respectively. When Azo/PEG complexes were dissolved in solvents, hydrogen-bonding interaction hindered the rotation and inversion of mesogens, causing a reduction in the photoisomerization rate compared with the photoisomerization rate of the neat Azo. The confinement of Azo/PEG complexes in thin films further resulted in a substantial decrease in the photoisomerization rate but an increase in the amounts of H-aggregated and J-aggregated mesogens. Regarding PEG crystallization, ultraviolet irradiation of Azo/PEG complexes increased the quantity of high-polarity cis isomers, which improved the compatibility between mesogens and PEG, subsequently increasing the crystallization temperature of PEG. Moreover, the complexation of Azo and PEG induced microphase separation, forming a lamellar morphology. Within the Azo-rich microphases, mesogens aggregated to form tilted monosmectic layers. By contrast, PEG crystallization within the PEG-rich microphases was hard confined, indicating that the domain size of the lamellar morphology was unchanged during PEG crystallization.

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“…The CN double bonds surrounding the CC backbones link each monomer and twist them to perform stable helix. The rigid rod helical conformation allows the polyisocyanide to be widely applied in chiral recognition, enantiomeric separation, and liquid crystallization . Helical polyisocyanides have been fabricated into block copolymers, grafted polymer brushes, and star polymers .…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of Helical Rod–Coil Block Polymers by the Combination of ATRP and Pd(II)‐Initiated Isocyanides Polymerizations

Liu

Jiang

et al. 2019

Macro Chemistry & Physics

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A bifunctional initiator containing propargyl bromoisobutyrate and alkyne‐Pd(II) (PBB‐Pd(II)) is designed and synthesized. The propargyl bromoisobutyrate unit of PBB‐Pd(II) can initiate the atom transfer radical polymerization (ATRP) of vinyl monomers, while the Pd(II) complex can initiate the polymerization of phenyl isocyanides. Both the ATRP and Pd(II)‐mediated isocyanide polymerization are proceeded in living/controlled manner. Thus, combining the two living polymerizations, a series of well‐defined block copolymers bearing rod poly(phenyl isocyanide)s and coil poly(acrylate) segments can be facilely prepared in high yield with tunable composition, controlled molar masses (Mns), and narrow molar mass distributions (Mw/Mns). What is more, benefiting from this synthetic strategy, well‐defined core cross‐linked star polymers are readily synthesized. Optically active block copolymers and star polymers can be facilely obtained by using chiral isocyanide monomers due to the formation of predominated one‐handed helix. The chiral star polymers show excellent enantioselective recognition ability in enantioselective crystallization of racemic compounds.

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Optically active helical polyisocyanides bearing chiral phosphine pendants: Facile synthesis and application in enantioselective Rauhut-Currier reaction

Cited by 25 publications

References 35 publications

Synthesis of Multi Amino Acid Chiral Polymeric Microparticles for Enantioselective Chemistry

Synthesis of Multi Amino Acid Chiral Polymeric Microparticles for Enantioselective Chemistry

Hydrogen Bonding-Induced Assembled Structures and Photoresponsive Behavior of Azobenzene Molecule/Polyethylene Glycol Complexes

Facile Synthesis of Helical Rod–Coil Block Polymers by the Combination of ATRP and Pd(II)‐Initiated Isocyanides Polymerizations

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