Polymerization Reactions Involving the Side Chains of α-L-Amino Acids

TY - JOUR

T1 - Polymerization Reactions Involving the Side Chains of α-L-Amino Acids

AU - Kohn, Joachim

AU - Langer, Robert

PY - 1987/2/1

Y1 - 1987/2/1

N2 - The feasibility of polymerizing naturally occurring α-L-amino acids via their side chains by bonds other than the amide bond was investigated. Poly(Pal-Hpr-ester) [IUPAC name: poly[(l-palmitoyl-4,2-pyrrolidinediyl)carbonyloxy]] was obtained by melt transesterification of N-Pal-Hpr-Me [IUPAC name: trans-4-hydroxyl-1-palmitoyl-L-proline methyl ester] in the presence of aluminum isopropoxide as catalyst. Mn(8450) and mw(15 500) were determined by gel permeation chromatography relative to polystyrene standards. The tyrosine dipeptide Z-Tyr-Tyr-Hex [IUPAC name: N-(N-benzyl-oxycarbonyl-L-tyrosyl)-L-tyrosine hexyl ester] was cyanylated at the tyrosine side chain hydroxyl groups to yield Z-Tyr-Tyr-Hex-dicyanate [IUPAC name: N-[N-benzyloxycarbony1-3-(p-cyanatopheny1)-L-alanyl]-3-(p-cyanatopheny1)-L-alanine hexyl ester]. By solution polymerization of equimolar quantities of Z-Tyr-Tyr-Hex and Z-Tyr-Tyr-Hex-dicyanate in tetra-hydrofuran, poly(Z-Tyr-Tyr-Hex-iminocarbonate) [IUPAC name: poly[oxyimidocarbonyloxy-p-phenylene[2-(hexyloxy-carbonyl)ethylene]imino[2-[l-(benzyloxy)formamido]-l-oxotrimethylene]-p-phenylene]] was obtained with Mn= 11 500 and mw= 19 500. The synthesis of such “pseudopoly(amino acids)”, which may be regarded as structural analogues of conventional poly(amino acids), may be of interest in enzymology, immunology, pharmacology, and biotechnology (biomaterials for medical applications).

AB - The feasibility of polymerizing naturally occurring α-L-amino acids via their side chains by bonds other than the amide bond was investigated. Poly(Pal-Hpr-ester) [IUPAC name: poly[(l-palmitoyl-4,2-pyrrolidinediyl)carbonyloxy]] was obtained by melt transesterification of N-Pal-Hpr-Me [IUPAC name: trans-4-hydroxyl-1-palmitoyl-L-proline methyl ester] in the presence of aluminum isopropoxide as catalyst. Mn(8450) and mw(15 500) were determined by gel permeation chromatography relative to polystyrene standards. The tyrosine dipeptide Z-Tyr-Tyr-Hex [IUPAC name: N-(N-benzyl-oxycarbonyl-L-tyrosyl)-L-tyrosine hexyl ester] was cyanylated at the tyrosine side chain hydroxyl groups to yield Z-Tyr-Tyr-Hex-dicyanate [IUPAC name: N-[N-benzyloxycarbony1-3-(p-cyanatopheny1)-L-alanyl]-3-(p-cyanatopheny1)-L-alanine hexyl ester]. By solution polymerization of equimolar quantities of Z-Tyr-Tyr-Hex and Z-Tyr-Tyr-Hex-dicyanate in tetra-hydrofuran, poly(Z-Tyr-Tyr-Hex-iminocarbonate) [IUPAC name: poly[oxyimidocarbonyloxy-p-phenylene[2-(hexyloxy-carbonyl)ethylene]imino[2-[l-(benzyloxy)formamido]-l-oxotrimethylene]-p-phenylene]] was obtained with Mn= 11 500 and mw= 19 500. The synthesis of such “pseudopoly(amino acids)”, which may be regarded as structural analogues of conventional poly(amino acids), may be of interest in enzymology, immunology, pharmacology, and biotechnology (biomaterials for medical applications).

UR - https://www.scopus.com/pages/publications/0001751316

UR - https://www.scopus.com/pages/publications/0001751316#tab=citedBy

U2 - 10.1021/ja00237a030

DO - 10.1021/ja00237a030

M3 - Article

SN - 0002-7863

VL - 109

SP - 817

EP - 820

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 3

ER -