Hydrolases in Polymer Chemistry: Chemoenzymatic Approaches to Polymeric Materials - Enzymatic Polymerisation - page 79

3 Chemoenzymatic Approaches to Chiral (Co)polymers ...................................... 95

3.1 Enantioselectivity Issues in Enzyme-Catalyzed Reactions ........................... 95

3.2 Reaction Mechanism and Enantioselectivity of Lipases ............................. 97

3.3 Enantioselective Ring-Opening Polymerizations of Substituted
Lactones Using Lipases................................................................ 101
3.4 Chiral Polymers by Chemoenzymatic Catalysis ...................................... 103
4 Conclusions .................................................................................... 110
References .......................................................................................... 111

Abbreviations

AT R P Atom transfer radical polymerization

CALB Candida antarctica Lipase B

CL ε -Caprolactone

DXO 1,5-Dioxepane-2-one

FOMA 1 H ,1 H ,2 H ,2 H -Perfluorooctyl methacrylate

FRP Free-radical polymerization

GMA Glydidyl methacrylate

GPEC Gradient polymer elution chromatography

HEA Hydroxyethyl acrylate

HEMA Hydroxyethyl methacrylate

LCCC Liquid chromatography under critical conditions

MMA Methyl methacrylate

NMP Nitroxide-mediated polymerization

PEG Poly(ethylene glycol)

PCL Poly( ε -caprolactone)

PMCL Poly(4-methyl- ε -caprolactone)

PGMA Poly(glydidyl methacrylate)

PPDL Poly( ω -pentadecalactone)

PTHF Poly(tetrahydrofurane)

RAFT Reversible addition-fragmentation chain transfer

ROP Ring-opening polymerization

scCO 2 Supercritical carbon dioxide

SEC Size-exclusion chromatography

1 Introduction

Chemists have developed numerous synthetic procedures to supply an ever-
increasing number of structurally and functionally diverse materials for advanced
application. Almost all of these procedures rely on efficient catalytic systems, which
allow the synthesis to be carried out at an economical time-scale. Most catalysts are
highly specific in terms of the chemical conversion they catalyze. Although this is
an advantage for the catalytic selectivity, it limits the general applicability of a cat-
alyst in multistep conversions. This can be overcome by the combination of several