Synthesis and Organocatalytic Ring-Opening Polymerization of Cyclic Esters Derived from L-Malic Acid

被引：61

作者：

Pounder, Ryan J. ^{[1
]}

Dove, Andrew P. ^{[1
]}

机构：

[1] Univ Warwick, Dept Chem, Coventry CV4 7AL, W Midlands, England

来源：

BIOMACROMOLECULES | 2010年 / 11卷 / 08期

基金：

英国工程与自然科学研究理事会;

关键词：

ALIPHATIC POLYESTERS; BIODEGRADABLE POLYMERS; BIOMEDICAL APPLICATIONS; EPSILON-CAPROLACTONE; RELEASE BEHAVIOR; DRUG-RELEASE; COPOLYMERS; LACTIDE; DEGRADATION; POLYLACTIDE;

D O I：

10.1021/bm1004355

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

The synthesis of 3-(S)-[(benzyloxycarbonyl)methyl]-1,4-dioxane-2,5-dione (BMD) and 3,6-(S)-[di(benzyloxycarbonyl)methyl]-1,4-dioxane-2,5-dione (malide) from commercially available L-malic acid is reported. Ring-opening polymerization (ROP) studies of BMD are reported showing that the controlled ROP of this monomer is possible in the absence of transesterification side reactions, despite the presence of side-chain esters, using 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea and (-)-sparteine to catalyze the polymerization. The ROP of malide with this system was ineffective. Investigation of the effect of initiating species revealed that the electronic nature of the alcohol had a greater effect on the ultimate molecular weight and hence initiator efficiency than steric considerations. Deprotection of the resultant poly(BMD) using H-2 and Pd/C resulted in hydrophilic poly(glycolic-co-malic acid)s (PGMAs) that were able to undergo autocatalytic degradation in dilute H2O solution such that complete degradation was observed within 6 days.

引用

页码：1930 / 1939

页数：10

共 59 条

[41]

OUCHI T, 1989, MAKROMOL CHEM, V190, P1523

[42] Aliphatic polyesters with pendant cyclopentene groups:: Controlled synthesis and conversion to polyester-graft-PEG copolymers [J].

Parrish, B ;

Emrick, T .

MACROMOLECULES, 2004, 37 (16) :5863-5865

[43] Towards poly(ester) nanoparticles: recent advances in the synthesis of functional poly(ester)s by ring-opening polymerization [J].

Pounder, Ryan J. ;

Dove, Andrew P. .

POLYMER CHEMISTRY, 2010, 1 (03) :260-271

[44] Exploration, optimization, and application of supramolecular thiourea-amine catalysts for the synthesis of lactide (co)polymers [J].

Pratt, Russell C. ;

Lohmeijer, Bas G. G. ;

Long, David A. ;

Lundberg, P. N. Pontus ;

Dove, Andrew P. ;

Li, Hongbo ;

Wade, Charles G. ;

Waymouth, Robert M. ;

Hedrick, James L. .

MACROMOLECULES, 2006, 39 (23) :7863-7871

[45] Synthesis of 2-azidoethyl α-D-mannopyranoside orthogonally protected and selective deprotections [J].

Reina, JJ ;

Rojo, J .

TETRAHEDRON LETTERS, 2006, 47 (15) :2475-2478

[46]

Shen YQ, 2000, J BIOMED MATER RES, V50, P528, DOI 10.1002/(SICI)1097-4636(20000615)50:4<528::AID-JBM8>3.0.CO

[47]

2-S

[48] Stereocontrolled ring-opening polymerisation of lactide [J].

Stanford, Matthew J. ;

Dove, Andrew P. .

CHEMICAL SOCIETY REVIEWS, 2010, 39 (02) :486-494

[49] Biomaterials from sugars: ring-opening polymerization of a carbohydrate lactone [J].

Tang, Min ;

White, Andrew J. P. ;

Stevens, Molly M. ;

Williams, Charlotte K. .

CHEMICAL COMMUNICATIONS, 2009, (08) :941-943

[50]

Tasaka F, 2001, MACROMOL RAPID COMM, V22, P820, DOI 10.1002/1521-3927(20010701)22:11<820::AID-MARC820>3.0.CO

← 1 2 3 4 5 6 →