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Dirigent Proteins from Cotton ( Gossypium sp.) for the Atropselective Synthesis of Gossypol
Author(s) -
Effenberger Isabelle,
Zhang Bin,
Li Ling,
Wang Qiang,
Liu Yuxiu,
Klaiber Iris,
Pfannstiel Jens,
Wang Qingmin,
Schaller Andreas
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201507543
Subject(s) - gossypol , enantiomer , chemistry , biosynthesis , atropisomer , stereochemistry , biochemistry , enzyme
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. (+)‐Gossypol predominates in vivo, thus suggesting stereochemically controlled biosynthesis. The aim was to identify the factors mediating (+)‐gossypol formation in cotton and to investigate their potential for asymmetric biaryl synthesis. A dirigent protein from Gossypium hirsutum (GhDIR4) was found to confer atropselectivity to the coupling of hemigossypol in presence of laccase and O 2 as an oxidizing agent. (+)‐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.