Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst

Jian Huang; Ling Shen; Hui Zou; Na Liu

doi:10.1007/s10118-018-2136-5

Your Location：

Home >

Browse articles >

Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst

RAPID COMMUNICATION | Updated：2021-02-18

- Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst
- Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst
- Chinese Journal of Polymer Science 2018年36卷第7期页码：799-804
- Affiliations：
  
  Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei 230009, China
- Author bio：
  
  liuna@hfut.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 51673057, 21622402, and 21574036). N. Liu thanks Anhui Provincial Natural Science Foundation (No. 1608085MB41).
- DOI：10.1007/s10118-018-2136-5
  中图分类号：
- 收稿：2018-02-09，
  
  录用：2018-3-26，
  
  网络首发：2018-04-28，
  
  纸质出版：2018-07
- Accepted：
Scan QR Code
Jian Huang, Ling Shen, Hui Zou, 等. Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst[J]. Chinese Journal of Polymer Science, 2018,36(7):799-804.

Jian Huang, Ling Shen, Hui Zou, et al. Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst[J]. Chinese Journal of Polymer Science, 2018, 36(7): 799-804.
Jian Huang, Ling Shen, Hui Zou, 等. Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst[J]. Chinese Journal of Polymer Science, 2018,36(7):799-804. DOI： 10.1007/s10118-018-2136-5.

Jian Huang, Ling Shen, Hui Zou, et al. Enantiomer-selective Living Polymerization of rac-Phenyl Isocyanide Using Chiral Palladium Catalyst[J]. Chinese Journal of Polymer Science, 2018, 36(7): 799-804. DOI： 10.1007/s10118-018-2136-5.

摘要

Abstract

We report the polymerization of phenyl isocyanides with the chiral palladium(II) initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer (

rac

-1)

and enantiomerically unbalanced polymerization of the monomer was found

providing substantial evidence for the enantiomer-selective polymerization of

rac

-1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers

4-isocyanobenzoyl-L-alanine decyl ester (1s) and 4-isocyanobenzoyl-D-alanine decyl ester (1r)

revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of 1s was higher than that of 1r with chiral ligands. The results clearly demonstrated the inclination for incorporation of the 1s enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated

and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium(II) catalyst. Moreover

the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.

关键词

Keywords

references

Okamoto, Y.; Suzuki, K.; Ohta, K.; Hatada, K.; Yuki, H . Optically active poly(triphenylmethyl methacrylate) with one-handed helical conformation . J. Am. Chem. Soc. , 1979 . 101 ( 16 ): 4763 - 4765 . DOI: 10.1021/ja00510a072 http://doi.org/10.1021/ja00510a072 .

Miyake, G. M.; Mariott, W. R.; Chen, E. Y. X . Asymmetric coordination polymerization of acrylamides by enantiomeric metallocenium ester enolate catalysts . J. Am. Chem. Soc. , 2007 . 129 ( 21 ): 6724 - 6725 . DOI: 10.1021/ja072073p http://doi.org/10.1021/ja072073p .

Wang, R.; Li, X. F.; Bai, J. W.; Zhang, J.; Liu, A. H.; Wan, X. H . Chiroptical and thermotropic properties of helical styrenic polymers: effect of achiral group . Macromolecules , 2014 . 47 ( 5 ): 1553 - 1562 . DOI: 10.1021/ma500147z http://doi.org/10.1021/ma500147z .

Cui, J. X.; Zhang, J.; Wan, X. H . Unexpected stereomutation dependence on the chemical structure of helical vinyl glycopolymers . Chem. Commun. , 2012 . 48 ( 36 ): 4341 - 4343 . DOI: 10.1039/c2cc00036a http://doi.org/10.1039/c2cc00036a .

Zhu, Y. Y.; Yin, T. T.; Li, X. L.; Su, M.; Xue, Y. X.; Yu, Z. P.; Liu, N.; Yin, J.; Wu, Z. Q . Synthesis and chiroptical properties of helical polyallenes bearing chiral amide pendants . Macromolecules , 2014 . 47 ( 20 ): 7021 - 7029 . DOI: 10.1021/ma5019022 http://doi.org/10.1021/ma5019022 .

Wu, Z. Q.; Radcliffe, J. D.; Ono, R. J.; Chen, Z.; Li, Z. C.; Bielawski, C. W . Synthesis of conjugated diblock copolymers: two mechanistically distinct, sequential living polymerizations using a single catalyst . Polym. Chem. , 2012 . 3 ( 4 ): 874 - 881 . DOI: 10.1039/c2py00566b http://doi.org/10.1039/c2py00566b .

Zhang, W. M.; Zhang, J.; Qiao, Z.; Yin, J . Functionally oriented tumor microenvironment responsive polymeric nanoassembly: engineering and applications . Chinese J. Polym. Sci. , 2018 . 36 ( 3 ): 273 - 287 . DOI: 10.1007/s10118-018-2035-9 http://doi.org/10.1007/s10118-018-2035-9 .

Makiguchi, W.; Kobayashi, S.; Furusho, Y.; Yashima, E . Formation of a homo double helix of a conjugated polymer with carboxy groups and amplification of the macromolecular helicity by chiral amines sandwiched between the strands . Angew. Chem. Int. Ed. , 2013 . 52 ( 20 ): 5275 - 5279 . DOI: 10.1002/anie.201301005 http://doi.org/10.1002/anie.201301005 .

Zhou, L.; Jiang, Z. Q.; Xu, N.; Liu, N.; Wu, Z. Q . Polythiophene-block-poly(phenyl isocyanide) copolymers: one-pot synthesis, properties and applications . Chinese J. Polym. Sci. , 2017 . 35 ( 12 ): 1447 - 1456 . DOI: 10.1007/s10118-017-2003-9 http://doi.org/10.1007/s10118-017-2003-9 .

Zhou, L.; Shen, L.; Huang, J.; Liu, N.; Zhu, Y. Y.; Wu, Z. Q . Optically active helical polyisocyanides bearing chiral phosphine pendants: facile synthesis and application in enantioselective Rauhut-Currier reaction . Chinese J. Polym. Sci. , 2018 . 36 ( 2 ): 163 - 170 . DOI: 10.1007/s10118-018-2044-8 http://doi.org/10.1007/s10118-018-2044-8 .

Green, M. M.; Peterson, N. C.; Sato, T.; Teramoto, A.; Cook, R.; Lifson, S . A helical polymer with a cooperative response to chiral information . Science , 1995 . 268 ( 5219 ): 1860 - 1866 . DOI: 10.1126/science.268.5219.1860 http://doi.org/10.1126/science.268.5219.1860 .

Li, J.; Schuster, G. B.; Cheon, K. S.; Green, M. M.; Selinger, J. V . Switching a helical polymer between mirror images using circularly polarized light . J. Am. Chem. Soc. , 2000 . 122 ( 11 ): 2603 - 2612 . DOI: 10.1021/ja993290w http://doi.org/10.1021/ja993290w .

Maeda, K.; Wakasone, S.; Shimomura, K.; Ikai, T.; Kanoh, S . Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant . Chem. Commun. , 2012 . 48 ( 27 ): 3342 - 3344 . DOI: 10.1039/c2cc00024e http://doi.org/10.1039/c2cc00024e .

Sakai, N.; Satoh, T.; Kakuchi, T . Rod-like amphiphile of diblock polyisocyanate leading to cylindrical micelle and spherical vesicle in water . Macromolecules , 2014 . 47 ( 5 ): 1699 - 1704 . DOI: 10.1021/ma500097t http://doi.org/10.1021/ma500097t .

Reuther, J. F.; DeSousa, J. D.; Novak, B. M . Direct probing of regioregularity for polycarbodiimide systems via 15 N NMR analysis . Macromolecules , 2012 . 45 ( 19 ): 7719 - 7728 . DOI: 10.1021/ma301448b http://doi.org/10.1021/ma301448b .

Reuther, J. F.; Novak, B. M . Evidence of entropy-driven bistability through 15 N NMR analysis of a temperature- and solvent-induced, chiroptical switching polycarbodiimide . J. Am. Chem. Soc. , 2013 . 135 ( 51 ): 19292 - 19303 . DOI: 10.1021/ja4098803 http://doi.org/10.1021/ja4098803 .

Budhathoki-Uprety, J.; Jena, P. V.; Roxbury, D.; Heller, D. A . Helical polycarbodiimide cloaking of carbon nanotubes enables inter-nanotube exciton energy transfer modulation . J. Am. Chem. Soc. , 2014 . 136 ( 44 ): 15545 - 15550 . DOI: 10.1021/ja505529n http://doi.org/10.1021/ja505529n .

Reuther, J. F.; Siriwardane, D. A.; Kulikov, O. V.; Batchelor, B. L.; Campos, R.; Novak, B. M . Facile synthesis of rod-coil block copolymers with chiral, helical polycarbodiimide segments via postpolymerization CuAAC " click” coupling of functional end groups . Macromolecules , 2015 . 48 ( 10 ): 3207 - 3216 . DOI: 10.1021/acs.macromol.5b00453 http://doi.org/10.1021/acs.macromol.5b00453 .

Liu, X.; Song, C.; Luo, X. F.; Yang, W. T.; Deng, J. P . " Sergeants and soldiers rule” in helical substitutedacetylene copolymer emulsions . Chinese J. Polym. Sci. , 2013 . 31 ( 1 ): 179 - 186 . DOI: 10.1007/s10118-013-1189-8 http://doi.org/10.1007/s10118-013-1189-8 .

Akagi, K . Helical polyacetylene: asymmetric polymerization in a chiral liquid-crystal field . Chem. Rev. , 2009 . 109 ( 11 ): 5354 - 5401 . DOI: 10.1021/cr900198k http://doi.org/10.1021/cr900198k .

Matsushita, S.; Kyotani, M.; Akagi, K . Hierarchically controlled helical graphite films prepared from iodine-doped helical polyacetylene films using morphology-retaining carbonization . J. Am. Chem. Soc. , 2011 . 133 ( 44 ): 17977 - 17992 . DOI: 10.1021/ja2082922 http://doi.org/10.1021/ja2082922 .

Sakai, R.; Sakai, N.; Satoh, T.; Li, W.; Zhang, A. F.; Kakuchi, T . Strict size specificity in colorimetric anion detection based on poly(phenylacetylene) receptor bearing second generation lysine dendrons . Macromolecules , 2011 . 44 ( 11 ): 4249 - 4257 . DOI: 10.1021/ma200710r http://doi.org/10.1021/ma200710r .

Li, S.; Liu, K.; Kuang, G. C.; Masuda, T.; Zhang, A. F . Thermoresponsive helical poly(phenylacetylene)s . Macromolecules , 2014 . 47 ( 10 ): 3288 - 3296 . DOI: 10.1021/ma5003529 http://doi.org/10.1021/ma5003529 .

Song, C.; Liu, X.; Liu, D.; Ren, C. L.; Yang, W. T.; Deng, J. P . Optically active particles of chiral polymers . Macromol. Rapid Commun. , 2013 . 34 ( 18 ): 1426 - 1445 . DOI: 10.1002/marc.v34.18 http://doi.org/10.1002/marc.v34.18 .

Rodríguez, R.; Quiñoá, E.; Riguera, R.; Freire, F . Architecture of chiral poly(phenylacetylene)s: from compressed/highly dynamic to stretched/quasi-static helices . J. Am. Chem. Soc. , 2016 . 138 ( 30 ): 9620 - 9628 . DOI: 10.1021/jacs.6b04834 http://doi.org/10.1021/jacs.6b04834 .

Zhao, Z. Y.; Wang, S.; Ye, X. C.; Zhang, J.; Wan, X. H . Planar-to-axial chirality transfer in the polymerization of phenylacetylenes . ACS Macro Lett. , 2017 . 6 ( 3 ): 205 - 209 . DOI: 10.1021/acsmacrolett.6b00901 http://doi.org/10.1021/acsmacrolett.6b00901 .

Wang, S.; Chen, J. X.; Feng, X. Y.; Shi, G.; Zhang, J.; Wan, X. H . Conformation shift switches the chiral amplification of helical copoly(phenylacetylene)s from abnormal to normal " sergeants- and-soldiers” effect . Macromolecules , 2017 . 50 ( 12 ): 4610 - 4615 . DOI: 10.1021/acs.macromol.7b01028 http://doi.org/10.1021/acs.macromol.7b01028 .

Yoshio, O.; Koji, O.; Heimei, Y . Highly asymmetric selective polymerization of ( RS )- α -methylbenzyl methacrylate by grignard reagent-(-)-sparteine catalyst systems . Chem. Lett. , 1977 . 6 ( 6 ): 617 - 620 . DOI: 10.1246/cl.1977.617 http://doi.org/10.1246/cl.1977.617 .

Okamoto, Y.; Urakawa, K.; Ohta, K.; Yuki, H . Asymmetric- selective polymerization of ( RS )- α -methylbenzyl methacrylate . Macromolecules , 1978 . 11 ( 4 ): 719 - 723 . DOI: 10.1021/ma60064a020 http://doi.org/10.1021/ma60064a020 .

Okamoto, Y.; Suzuki, K.; Kitayama, T.; Yuki, H.; Kageyama, H.; Miki, K.; Tanaka, N.; Kasai, N . Kinetic resolution of racemic alpha-methylbenzyl methacrylate: asymmetric selective polymeriza-tion catalyzed by Grignard reagent-(-)-sparteine derivative complexes . J. Am. Chem. Soc. , 1982 . 104 ( 17 ): 4618 - 4624 . DOI: 10.1021/ja00381a019 http://doi.org/10.1021/ja00381a019 .

Spassky, N.; Wisniewski, M.; Pluta, C.; Le Borgne, A . Highly stereoelective polymerization of rac -(D,L)-lactide with a chiral schiff's base/aluminium alkoxide initiator . Macromol. Chem. Phys. , 1996 . 197 ( 9 ): 2627 - 2637 . DOI: 10.1002/macp.1996.021970902 http://doi.org/10.1002/macp.1996.021970902 .

Boucard, V.; Dumas, P.; Sigwalt, P.; Guérin, P.; Fadel, A . Living stereospecific and enantioasymmetric polymerization of methylthiirane initiated by various bis(alkyl- S -cysteinato) cadmium . Eur. Polym. J. , 1996 . 32 ( 4 ): 481 - 485 . DOI: 10.1016/0014-3057(95)00155-7 http://doi.org/10.1016/0014-3057(95)00155-7 .

Imai, T.; Hayakawa, K.; Satoh, T.; Kaga, H.; Kakuchi, T . Enantiomer-selective polymerization of ( RS )-(phenoxymethyl) thiirane with diethylzinc/L-amino acid . J. Polym. Sci., Part A: Polym. Chem. , 2002 . 40 ( 20 ): 3443 - 3448 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

Tsuji, M.; Aoki, T.; Sakai, R.; Satoh, T.; Kaga, H.; Kakuchi, T . Enantiomer-selective radical cyclopolymerization of rac -2,4- pentanediyl dimethacrylate using a ruthenium-mediated chiral atom transfer radical polymerization initiating system . J. Polym. Sci., Part A: Polym. Chem. , 2004 . 42 ( 18 ): 4563 - 4569 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

Hirahata, W.; Thomas, R. M.; Lobkovsky, E. B.; Coates, G. W . Enantioselective polymerization of epoxides: a highly active and selective catalyst for the preparation of stereoregular polyethers and enantiopure epoxides . J. Am. Chem. Soc. , 2008 . 130 ( 52 ): 17658 - 17659 . DOI: 10.1021/ja807709j http://doi.org/10.1021/ja807709j .

Thomas, R. M.; Widger, P. C. B.; Ahmed, S. M.; Jeske, R. C.; Hirahata, W.; Lobkovsky, E. B.; Coates, G. W . Enantioselective epoxide polymerization using a bimetallic cobalt catalyst . J. Am. Chem. Soc. , 2010 . 132 ( 46 ): 16520 - 16525 . DOI: 10.1021/ja1058422 http://doi.org/10.1021/ja1058422 .

Zhu, H.; Luo, S. Z.; Wu, Z. Q . Living and enantiomer-selective polymerization of allene initiated by Ni complex containing chiral phosphine . Chin. Chem. Lett. , 2018 . DOI: 10.1016/j.cclet.2018.03.002 DOI: 10.1016/j.cclet.2018.03.002 http://doi.org/10.1016/j.cclet.2018.03.002 .

Makiguchi, K.; Yamanaka, T.; Kakuchi, T.; Terada, M.; Satoh, T . Binaphthol-derived phosphoric acids as efficient chiral organocatalysts for the enantiomer-selective polymerization of rac -lactide . Chem. Commun. , 2014 . 50 ( 22 ): 2883 - 2885 . DOI: 10.1039/C4CC00215F http://doi.org/10.1039/C4CC00215F .

Li, H.; Ai, B. R.; Hong, M . Stereoselective ring-opening poly- merization of rac -lactide by bulky chiral and achiral N -hetero- cyclic carbenes . Chinese J. Polym. Sci. , 2017 . 36 ( 2 ): 231 - 236 . .

Zhao, W.; Li, C. Y.; Wu, C. J.; Liu, X. L.; Mou, Z. H.; Yao, C. G.; Cui, D. M . Synthesis of ultraviolet absorption polylactide via immortal polymerization of rac -lactide initiated by a Salan- yttrium catalyst . Chinese J. Polym. Sci. , 2017 . 36 ( 2 ): 202 - 206 . .

Zhong, Z. Y.; Dijkstra, P. J.; Feijen, J . Controlled and stereo- selective polymerization of lactide: kinetics, selectivity, and micro- structures . J. Am. Chem. Soc. , 2003 . 125 ( 37 ): 11291 - 11298 . DOI: 10.1021/ja0347585 http://doi.org/10.1021/ja0347585 .

Ahmed, S. M.; Poater, A.; Childers, M. I.; Widger, P. C. B.; LaPointe, A. M.; Lobkovsky, E. B.; Coates, G. W.; Cavallo, L . Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: a mechanistic study . J. Am. Chem. Soc. , 2013 . 135 ( 50 ): 18901 - 18911 . DOI: 10.1021/ja409521z http://doi.org/10.1021/ja409521z .

Xue, Y. X.; Zhu, Y. Y.; Gao, L. M.; He, X. Y.; Liu, N.; Zhang, W. Y.; Yin, J.; Ding, Y. S.; Zhou, H. P.; Wu, Z. Q . Air-stable (phenylbuta-1,3-diynyl)palladium(II) complexes: highly active initiators for living polymerization of isocyanides . J. Am. Chem. Soc. , 2014 . 136 ( 12 ): 4706 - 4713 . DOI: 10.1021/ja5004747 http://doi.org/10.1021/ja5004747 .

Chen, J. L.; Yang, L.; Wang, Q.; Jiang, Z. Q.; Liu, N.; Yin, J.; Ding, Y. S.; Wu, Z. Q . Helix-sense-selective and enantiomer- selective living polymerization of phenyl isocyanide induced by reusable chiral lactide using achiral palladium initiator . Macromolecules , 2015 . 48 ( 21 ): 7737 - 7746 . DOI: 10.1021/acs.macromol.5b02124 http://doi.org/10.1021/acs.macromol.5b02124 .

Zhou, W.; Su, X.; Tao, M. N.; Zhu, C. Z.; Zhao, Q. J.; Zhang, J. L . Chiral sulfinamide bisphosphine catalysts: design, synthesis, and application in highly enantioselective intermolecular cross- rauhut-currier reactions . Angew. Chem. Int. Ed. , 2015 . 54 ( 49 ): 14853 - 14857 . DOI: 10.1002/anie.201508108 http://doi.org/10.1002/anie.201508108 .

Zhang, Z. M.; Chen, P.; Li, W. B.; Niu, Y. F.; Zhao, X. L.; Zhang, J. L . A new type of chiral sulfinamide monophosphine ligands: stereodivergent synthesis and application in enantio- selective gold(I)-catalyzed cycloaddition reactions . Angew. Chem. Int. Ed. , 2014 . 53 ( 17 ): 4350 - 4354 . DOI: 10.1002/anie.201401067 http://doi.org/10.1002/anie.201401067 .

Kajitani, T.; Okoshi, K.; Sakurai, S. I.; Kumaki, J.; Yashima, E . Helix-sense controlled polymerization of a single phenyl iso-cyanide enantiomer leading to diastereomeric helical polyiso-cyanides with opposite helix-sense and cholesteric liquid crystals with opposite twist-sense . J. Am. Chem. Soc. , 2006 . 128 ( 3 ): 708 - 709 . DOI: 10.1021/ja0576536 http://doi.org/10.1021/ja0576536 .

Okamoto, Y.; Urakawa, K.; Yuki, H . Asymmetric selective polymerization of racemic methacrylates with the cyclo- hexylmagnesium bromide-(-)-sparteine system . J. Polym. Sci., Polym. Chem. Ed. , 1981 . 19 ( 6 ): 1385 - 1395 . DOI: 10.1002/pol.1981.170190611 http://doi.org/10.1002/pol.1981.170190611 .

Horeau, A . Interactions between enantiomers in solution; effect on the rotatory power . Optical purity and enantiomeric purity. Tetrahedron Lett. , 1969 . 36 3121 - 3124 . .

浏览量

273

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Optically Active Helical Poly(phenyl isocyanide)s Bearing Achiral Benzanilide Pendants: from Controlled Synthesis to Enantioseparation Application

Chiral Recognition and Resolution Based on Helical Polymers

Polythiophene-block-poly(phenyl isocyanide) Copolymers:One-pot Synthesis, Properties and Applications

A Facile and Environment-friendly Method for Fabrication of Polymer Brush

On-demand Peelable UV-curable Adhesives with Superior Bonding Strength: Rational Molecular Engineering of Cohesion-adhesion Synergy