Citation: Li Zhou, Ling Shen, Jian Huang, Na Liu, Yuan-Yuan Zhu, Zong-Quan Wu. Optically Active Helical Polyisocyanides Bearing Chiral Phosphine Pendants: Facile Synthesis and Application in Enantioselective Rauhut-Currier Reaction[J]. Chinese Journal of Polymer Science, ;2018, 36(2): 163-170. doi: 10.1007/s10118-018-2044-8 shu

Optically Active Helical Polyisocyanides Bearing Chiral Phosphine Pendants: Facile Synthesis and Application in Enantioselective Rauhut-Currier Reaction

Li Zhou ^a,b ,
Ling Shen ^a ,
Jian Huang ^a ,
Na Liu ^a,, ,
Yuan-Yuan Zhu ^a ,
Zong-Quan Wu ^a,,

a.
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei 230009, China
b.
School of Material and Chemical Engineering, Bengbu University, Bengbu 233030, China

Corresponding author: Na Liu, liuna@hfut.edu.cn Zong-Quan Wu, zqwu@hfut.edu.cn
Received Date: 29 August 2017
Accepted Date: 16 September 2017
Available Online: 10 November 2017

Three novel enantiopure phenyl isocyanide monomers with BH₃-protected phosphine functional group were designed and synthesized. Polymerization of these monomers using a alkyne-Pd(Ⅱ) complex as a catalyst led to the formation of respective helical polyisocyanides in high yields with controlled molecular weights (M_ns) and narrow molecular weight distributions (M_w/M_ns). Removing the protecting BH₃ groups afforded helical poly(phenyl isocyanide)s bearing phosphine pendants. Thanks to the chiral induction of monomer, the isolated helical polyisocyanides showed high optical activity, as revealed by circular dichroism (CD) and absorption spectroscopies and polarimetry. The helical structures of these polymers were quite stable in various organic solvents with different polarities and in a wide temperature range. Moreover, these helical polymers could be used as organocatalysts and showed good performance in enantioselective cross Rauhut-Currier reaction. The enantiomeric excess (ee) values of the isolated products of cross Rauhut-Currier reaction could be up to 90%. The polymer organocatalysts could be easily recovered from the reaction mixtures and reused at least five times in the reaction without significant loss of their enantioselectivities and catalytic activities.
- Helical polymer,
- Polyisocyanide,
- Coordination polymerization,
- Polymer catalyst
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