BioChem - DOS

Dirigent proteins from cotton (Gossypium sp.) for the atropselective synthesis of gossypol

Angewandte Chemie. international edition

Effenberger, Isabelle; Zhang, Bin; Li, Ling; Wang, Qiang; Liu, Yuxiu; Klaiber, Iris; Pfannstiel, Jens; Wang, Qingmin; Schaller, Andreas

<P><B>Abstract</B></P><P>Gossypol is a defense compound in cotton plants for protection against pests and pathogens. Gossypol biosynthesis involves the oxidative coupling of hemigossypol and results in two atropisomers owing to hindered rotation around the central binaphthyl bond. (+)&#8208;Gossypol predominates in vivo, thus suggesting stereochemically controlled biosynthesis. The aim was to identify the factors mediating (+)&#8208;gossypol formation in cotton and to investigate their potential for asymmetric biaryl synthesis. A dirigent protein from <I>Gossypium hirsutum</I> (GhDIR4) was found to confer atropselectivity to the coupling of hemigossypol in presence of laccase and O<SUB>2</SUB> as an oxidizing agent. (+)&#8208;Gossypol was obtained in greater than 80 % enantiomeric excess compared to racemic gossypol in the absence of GhDIR4. The identification of GhDIR4 highlights a broader role for DIRs in plant secondary metabolism and may eventually lead to the development of DIRs as tools for the synthesis of axially chiral binaphthyls.</P>

2015

WILEY&#x2010;VCH Verlag

1433-7851

1521-3773

54

49

pp.14660-14663

10.1002/anie.201507543

http://click.ndsl.kr/servlet/OpenAPIDetailView?keyValue=05787966&target=NART&cn=NART74763794

biaryls; biosynthesis; C&#xf8ff; C coupling; dirigent protein; enantioselectivity;