The effect of P-chiral center on helical conformation of optically active N-propargylphosphonamidates

Lihua Lu; Jiaoli Mo; Qiang Yang; Liqun Zhang; Weimin Wang; Dongmei Yue

doi:10.1515/epoly.2012.12.1.367

The effect of P-chiral center on helical conformation of optically active N-propargylphosphonamidates

Lihua Lu
, Jiaoli Mo
, Qiang Yang
, Liqun Zhang
, Weimin Wang
, Dongmei Yue

Beijing University of Chemical Technology
Abon Pharmaceuticals LLC

Research output: Contribution to journal › Article › peer-review

Abstract

Novel chiral and achiral N-propargylphosphonamidate monomers [HC=CCH ₂NH(P-O)R₁R₂,where 1: R₁=CH ₃,R₂=NHC(CH₃)₃ 2: R ₁=CH₃,R₂ =NHC₅H₉ 3:R ₁=OPh,R₂=NHC(CH₃)₃, 4:R ₁=R₂=OPh] were synthesized by successive condensation in order to study the helical conformation properties of N-phosphonamidates. One diastereomer was successfully separated from the other in the cases of monomer 1-3(named 1a-3a) according to the single peak in the ³¹P NMR spectra. Polymerizations of the monomers 1-4 were carried out with (nbd)Rh ⁺[η ⁶-C₆H₅B^-(C ₆H₅)₃] as catalyst in CHCl3 yielding the polymers with number-average molecular weights of 1300-22400. Poly(1a)-poly(3a) and poly(4) were characterized by UV and CD spectroscopy. Poly(1a)- poly(3a) showed an intense positive CD signal at 325 nm based on the conjugated polyacetylene backbone while poly(4) showed no peak there, indicating that the polymers had a helical structure with predominantly one-handed screw sense because of P-chiral centre sole contribution.

Original language	English
Article number	031
Journal	E-Polymers
DOIs	https://doi.org/10.1515/epoly.2012.12.1.367
State	Published - 15 Mar 2012
Externally published	Yes

Keywords

Helical polymer
N-propargylphosphonamidate
Optical activity
P-chiral center

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10.1515/epoly.2012.12.1.367

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@article{f20a1596b309444ebad19a40ff3ba32d,

title = "The effect of P-chiral center on helical conformation of optically active N-propargylphosphonamidates",

abstract = "Novel chiral and achiral N-propargylphosphonamidate monomers [HC=CCH 2NH(P-O)R1R2,where 1: R1=CH 3,R2=NHC(CH3)3 2: R 1=CH3,R2 =NHC5H9 3:R 1=OPh,R2=NHC(CH3)3, 4:R 1=R2=OPh] were synthesized by successive condensation in order to study the helical conformation properties of N-phosphonamidates. One diastereomer was successfully separated from the other in the cases of monomer 1-3(named 1a-3a) according to the single peak in the 31P NMR spectra. Polymerizations of the monomers 1-4 were carried out with (nbd)Rh +[η 6-C6H5B-(C 6H5)3] as catalyst in CHCl3 yielding the polymers with number-average molecular weights of 1300-22400. Poly(1a)-poly(3a) and poly(4) were characterized by UV and CD spectroscopy. Poly(1a)- poly(3a) showed an intense positive CD signal at 325 nm based on the conjugated polyacetylene backbone while poly(4) showed no peak there, indicating that the polymers had a helical structure with predominantly one-handed screw sense because of P-chiral centre sole contribution.",

keywords = "Helical polymer, N-propargylphosphonamidate, Optical activity, P-chiral center",

author = "Lihua Lu and Jiaoli Mo and Qiang Yang and Liqun Zhang and Weimin Wang and Dongmei Yue",

year = "2012",

month = mar,

day = "15",

doi = "10.1515/epoly.2012.12.1.367",

language = "英语",

journal = "E-Polymers",

issn = "1618-7229",

publisher = "Walter de Gruyter GmbH",

}

TY - JOUR

T1 - The effect of P-chiral center on helical conformation of optically active N-propargylphosphonamidates

AU - Lu, Lihua

AU - Mo, Jiaoli

AU - Yang, Qiang

AU - Zhang, Liqun

AU - Wang, Weimin

AU - Yue, Dongmei

PY - 2012/3/15

Y1 - 2012/3/15

N2 - Novel chiral and achiral N-propargylphosphonamidate monomers [HC=CCH 2NH(P-O)R1R2,where 1: R1=CH 3,R2=NHC(CH3)3 2: R 1=CH3,R2 =NHC5H9 3:R 1=OPh,R2=NHC(CH3)3, 4:R 1=R2=OPh] were synthesized by successive condensation in order to study the helical conformation properties of N-phosphonamidates. One diastereomer was successfully separated from the other in the cases of monomer 1-3(named 1a-3a) according to the single peak in the 31P NMR spectra. Polymerizations of the monomers 1-4 were carried out with (nbd)Rh +[η 6-C6H5B-(C 6H5)3] as catalyst in CHCl3 yielding the polymers with number-average molecular weights of 1300-22400. Poly(1a)-poly(3a) and poly(4) were characterized by UV and CD spectroscopy. Poly(1a)- poly(3a) showed an intense positive CD signal at 325 nm based on the conjugated polyacetylene backbone while poly(4) showed no peak there, indicating that the polymers had a helical structure with predominantly one-handed screw sense because of P-chiral centre sole contribution.

AB - Novel chiral and achiral N-propargylphosphonamidate monomers [HC=CCH 2NH(P-O)R1R2,where 1: R1=CH 3,R2=NHC(CH3)3 2: R 1=CH3,R2 =NHC5H9 3:R 1=OPh,R2=NHC(CH3)3, 4:R 1=R2=OPh] were synthesized by successive condensation in order to study the helical conformation properties of N-phosphonamidates. One diastereomer was successfully separated from the other in the cases of monomer 1-3(named 1a-3a) according to the single peak in the 31P NMR spectra. Polymerizations of the monomers 1-4 were carried out with (nbd)Rh +[η 6-C6H5B-(C 6H5)3] as catalyst in CHCl3 yielding the polymers with number-average molecular weights of 1300-22400. Poly(1a)-poly(3a) and poly(4) were characterized by UV and CD spectroscopy. Poly(1a)- poly(3a) showed an intense positive CD signal at 325 nm based on the conjugated polyacetylene backbone while poly(4) showed no peak there, indicating that the polymers had a helical structure with predominantly one-handed screw sense because of P-chiral centre sole contribution.

KW - Helical polymer

KW - N-propargylphosphonamidate

KW - Optical activity

KW - P-chiral center

UR - https://www.scopus.com/pages/publications/84858975985

U2 - 10.1515/epoly.2012.12.1.367

DO - 10.1515/epoly.2012.12.1.367

M3 - 文章

AN - SCOPUS:84858975985

SN - 1618-7229

JO - E-Polymers

JF - E-Polymers

M1 - 031

ER -

The effect of P-chiral center on helical conformation of optically active N-propargylphosphonamidates

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Keywords

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