title: Dirigent Proteins from Cotton (Gossypium sp.) for the Atropselective Synthesis of Gossypol.
abstract: 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 O2 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.
authors.affiliation: Institut für Physiologie und Biotechnologie der Pflanzen, Universität Hohenheim (260), 70593 Stuttgart (Germany).
authors.forename: Isabelle
authors.initials: I
authors.lastname: Effenberger
authors.affiliation: State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (P.R. China).
authors.forename: Bin
authors.initials: B
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (P.R. China).
authors.forename: Ling
authors.initials: L
authors.lastname: Li
authors.affiliation: State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (P.R. China).
authors.forename: Qiang
authors.initials: Q
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (P.R. China).
authors.forename: Yuxiu
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Serviceeinheit Massenspektrometrie, Universität Hohenheim (690), 70593 Stuttgart (Germany).
authors.forename: Iris
authors.initials: I
authors.lastname: Klaiber
authors.affiliation: Serviceeinheit Massenspektrometrie, Universität Hohenheim (690), 70593 Stuttgart (Germany).
authors.forename: Jens
authors.initials: J
authors.lastname: Pfannstiel
authors.affiliation: State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (P.R. China). wangqm@nankai.edu.cn.
authors.forename: Qingmin
authors.initials: Q
authors.lastname: Wang
authors.affiliation: Institut für Physiologie und Biotechnologie der Pflanzen, Universität Hohenheim (260), 70593 Stuttgart (Germany). andreas.schaller@uni-hohenheim.de.
authors.forename: Andreas
authors.initials: A
authors.lastname: Schaller
mesh_terms: D003368:Gossypium / Q000737:chemistry*; D006072:Gossypol / Q000096:biosynthesis* / Q000737:chemistry; D015394:Molecular Structure; D010940:Plant Proteins / Q000737:chemistry / Q000378:metabolism*
chemical_list: D010940:Plant Proteins; D006072:Gossypol
keywords: CC coupling; biaryls; biosynthesis; dirigent protein; enantioselectivity