Oxidative rearrangement of (+)-sesamin by CYP92B14 co-generates twin dietary lignans in sesame

Jun Murata, Eiichiro Ono, Seigo Yoroizuka, Hiromi Toyonaga, Akira Shiraishi, Shoko Mori, Masayuki Tera, Toshiaki Azuma, Atsushi J. Nagano, Masaru Nakayasu, Masaharu Mizutani, Tatsuya Wakasugi, Masayuki P. Yamamoto () and Manabu Horikawa ()
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Jun Murata: Suntory Foundation for Life Sciences (SUNBOR), 8-1-1 Seikadai, Seika
Eiichiro Ono: Research Institute, Suntory Global Innovation Center Ltd (SIC), 8-1-1 Seikadai, Seika
Seigo Yoroizuka: University of Toyama
Hiromi Toyonaga: Research Institute, Suntory Global Innovation Center Ltd (SIC), 8-1-1 Seikadai, Seika
Akira Shiraishi: Suntory Foundation for Life Sciences (SUNBOR), 8-1-1 Seikadai, Seika
Shoko Mori: Suntory Foundation for Life Sciences (SUNBOR), 8-1-1 Seikadai, Seika
Masayuki Tera: Suntory Foundation for Life Sciences (SUNBOR), 8-1-1 Seikadai, Seika
Toshiaki Azuma: Suntory Foundation for Life Sciences (SUNBOR), 8-1-1 Seikadai, Seika
Atsushi J. Nagano: Ryukoku University, 1-5 Yokotani, Seta Oe, Otsu
Masaru Nakayasu: Kobe University
Masaharu Mizutani: Kobe University
Tatsuya Wakasugi: University of Toyama
Masayuki P. Yamamoto: University of Toyama
Manabu Horikawa: Suntory Foundation for Life Sciences (SUNBOR), 8-1-1 Seikadai, Seika

Nature Communications, 2017, vol. 8, issue 1, 1-10

Abstract: Abstract (+)-Sesamin, (+)-sesamolin, and (+)-sesaminol glucosides are phenylpropanoid-derived specialized metabolites called lignans, and are rich in sesame (Sesamum indicum) seed. Despite their renowned anti-oxidative and health-promoting properties, the biosynthesis of (+)-sesamolin and (+)-sesaminol remained largely elusive. Here we show that (+)-sesamolin deficiency in sesame is genetically associated with the deletion of four C-terminal amino acids (Del4C) in a P450 enzyme CYP92B14 that constitutes a novel clade separate from sesamin synthase CYP81Q1. Recombinant CYP92B14 converts (+)-sesamin to (+)-sesamolin and, unexpectedly, (+)-sesaminol through an oxygenation scheme designated as oxidative rearrangement of α-oxy-substituted aryl groups (ORA). Intriguingly, CYP92B14 also generates (+)-sesaminol through direct oxygenation of the aromatic ring. The activity of CYP92B14 is enhanced when co-expressed with CYP81Q1, implying functional coordination of CYP81Q1 with CYP92B14. The discovery of CYP92B14 not only uncovers the last steps in sesame lignan biosynthesis but highlights the remarkable catalytic plasticity of P450s that contributes to metabolic diversity in nature.

Date: 2017
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Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_s41467-017-02053-7

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DOI: 10.1038/s41467-017-02053-7

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