BioChem - DOS

An Enzyme Cascade Synthesis of ε-Caprolactone and its Oligomers

Angewandte Chemie. international edition

Schmidt, Sandy; Scherkus, Christian; Muschiol, Jan; Menyes, Ulf; Winkler, Till; Hummel, Werner; Grö ger, Harald; Liese, Andreas; Herz, Hans‐ Georg; Bornscheuer, Uwe T.

<P><B>Abstract</B></P><P>Poly&#8208;&epsilon;&#8208;caprolactone (PCL) is chemically produced on an industrial scale in spite of the need for hazardous peracetic acid as an oxidation reagent. Although Baeyer&ndash;Villiger monooxygenases (BVMO) in principle enable the enzymatic synthesis of &epsilon;&#8208;caprolactone (&epsilon;&#8208;CL) directly from cyclohexanone with molecular oxygen, current systems suffer from low productivity and are subject to substrate and product inhibition. The major limitations for such a biocatalytic route to produce this bulk chemical were overcome by combining an alcohol dehydrogenase with a BVMO to enable the efficient oxidation of cyclohexanol to &epsilon;&#8208;CL. Key to success was a subsequent direct ring&#8208;opening oligomerization of in situ formed &epsilon;&#8208;CL in the aqueous phase by using lipase A from Candida antarctica, thus efficiently solving the product inhibition problem and leading to the formation of oligo&#8208;&epsilon;&#8208;CL at more than 20&#8197;g&thinsp;<SMALL>L</SMALL><SUP>&minus;1</SUP> when starting from 200&#8197;m<SMALL>M</SMALL> cyclohexanol. This oligomer is easily chemically polymerized to PCL.</P>

2015

1433-7851

1521-3773

54

9

pp.2784-2787

10.1002/anie.201410633

http://click.ndsl.kr/servlet/OpenAPIDetailView?keyValue=05787966&target=NART&cn=NART71475982

Baeyer&ndash; Villiger monooxygenases; cascade reactions; &epsilon; &#8208; caprolactone; enzyme catalysis; polymer synthesis;