Biosynthesis of Lycosantalonol, a cis-Prenyl Derived Diterpenoid

dc.contributor.author Zi, Jiachen
dc.contributor.author Matsuba, Yuki
dc.contributor.author Hong, Young
dc.contributor.author Jackson, Alana
dc.contributor.author Tantillo, Dean
dc.contributor.author Pichersky, Eran
dc.contributor.author Peters, Reuben
dc.contributor.department Biochemistry, Biophysics and Molecular Biology
dc.date 2020-04-02T15:17:08.000
dc.date.accessioned 2020-06-29T23:47:18Z
dc.date.available 2020-06-29T23:47:18Z
dc.date.copyright Wed Jan 01 00:00:00 UTC 2014
dc.date.embargo 2014-12-12
dc.date.issued 2014-01-01
dc.description.abstract <p>Terpenoid natural products are generally derived from isoprenyl diphosphate precursors with trans double-bond configuration, and no diterpenoid derived from the cisoid precursor (<em>Z</em>,<em>Z</em>,<em>Z</em>)-nerylneryl diphosphate (<strong>1</strong>) has yet been identified. Here further investigation of a terpenoid biosynthetic gene cluster from tomato is reported, which resulted in identification of a biosynthetic pathway from <strong>1</strong>, in a pathway featuring a number of interesting transformations. Compound <strong>1</strong> is first cyclized to a tricyclene core ring structure analogous to that found in α-santalene, with the resulting diterpene termed here lycosantalene (<strong>2</strong>). Quantum chemical calculations indicate a role for the diphosphate anion coproduct in this cyclization reaction. Subsequently, the internal cis double bond of the neryl side chain in <strong>2</strong> is then further transformed to an α-hydroxy ketone moiety via an epoxide intermediate (<strong>3</strong>). Oxygen labeling studies indicate <strong>3</strong> undergoes oxidative conversion to lycosantalonol (<strong>4</strong>). Thus, in addition to elucidating the cisoid origins of <strong>4</strong>, this work has further provided mechanistic insight into the interesting transformations required for its production.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>Journal of the American Chemical Society</em> 136 (2014): 16951, doi:<a href="http://dx.doi.org/10.1021/ja508477e" target="_blank">10.1021/ja508477e</a>. Copyright 2014 American Chemical Society.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/bbmb_ag_pubs/6/
dc.identifier.articleid 1012
dc.identifier.contextkey 6459466
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath bbmb_ag_pubs/6
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/10792
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/bbmb_ag_pubs/6/0-2014_Peters_BiosynthesisLycosantalonolLicense.pdf|||Sat Jan 15 01:06:15 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/bbmb_ag_pubs/6/2014_Peters_BiosynthesisLycosantalonol.pdf|||Sat Jan 15 01:06:17 UTC 2022
dc.source.uri 10.1021/ja508477e
dc.subject.disciplines Biochemistry, Biophysics, and Structural Biology
dc.subject.disciplines Genetics and Genomics
dc.subject.disciplines Natural Products Chemistry and Pharmacognosy
dc.subject.keywords diphosphate
dc.subject.keywords terpenoid
dc.subject.keywords cisoid
dc.title Biosynthesis of Lycosantalonol, a cis-Prenyl Derived Diterpenoid
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication 498a24ec-81d7-4bee-b145-323d38e7a392
relation.isOrgUnitOfPublication c70f85ae-e0cd-4dce-96b5-4388aac08b3f
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